US 2003OO69374A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2003/0069374A1 Grubbs et al. (43) Pub. Date: Apr. 10, 2003

(54) HEXACOORDINATED RUTHENIUM OR OSMIUM METAL METATHESIS CATALYSTS L R1 L R1 X. M X. M (75) Inventors: Robert H. Grubbs, South Pasadena, L-C= V and L-yc-c= V CA (US); Melanie S. Sanford, X 1. R X1. R Pasadena, CA (US); Jason L. Moore, Huntsville, CA (US); Jennifer A. Love, Pasadena, CA (US); Tina M. Trnka, wherein: Pasadena, CA (US) M is ruthenium or osmium; Correspondence Address: Pillsbury Winthrop LLP X and X’ are the same or different and are each Intellectual Property Group independently an anionic ; Suite 2800 725 South Figueroa Street L., Land L are the same or different and are each Los Angeles, CA 90017-5406 (US) independently a neutral electron donor ligand; and, (73) Assignee: California Institute of Technology and R and R' are each independently hydrogen or a Sub Cymetech, LLP Stituent Selected from the group consisting of C-Co , C2-Co alkenyl, Ca-Co alkynyl, aryl, C-C20 (21) Appl. No.: 10/172,765 carboxylate, C-Co alkoxy, C2-Co alkenyloxy, C-Co alkynyloxy, aryloxy, C.-Co alkoxycarbonyl, (22) Filed: Jun. 14, 2002 C-C alkylthio, C-Co alkylsulfonyl and C-Co alkylsulfinyl and silyl. Optionally, each of the R or Related U.S. Application Data R. Substituent group may be substituted with one or more moieties Selected from the group consisting of (63) Continuation-in-part of application No. 10/017,489, C-Co alkyl, C-Co alkoxy, and aryl which in turn filed on Dec. 14, 2001. may each be further substituted with one or more (60) Provisional application No. 60/314,978, filed on Aug. groups selected from a halogen, a C-C alkyl, C-Cs 24, 2001. Provisional application No. 60/309,806, alkoxy, and phenyl. Moreover, any of the catalyst filed on Aug. 1, 2001. may further include one or more functional groups. Examples of Suitable functional groups Publication Classification include but are not limited to: hydroxyl, , thio , , , , ether, , , (51) Int. Cl." ...... C08F 4/80; CO7F 15/00 , nitro, , , carbonate, (52) U.S. Cl...... 526/171; 556/136 , carbodiimide, carboalkoxy, , halogen, , , , , (57) ABSTRACT , ketal, boronate, cyano, cyanohydrin, hydra The present invention relates to novel hexacoordinated Zine, enamine, , , and Sulfenyl. In metathesis catalysts and to methods for making and using certain embodiments, at least one of L, L'and L is the same. The inventive catalysts are of the formula an N-heterocyclic carbene ligand. US 2003/0069374A1 Apr. 10, 2003

HEXACOORDINATED RUTHENIUM OR OSMUM METAL CARBENE METATHESIS CATALYSTS -continued L R1 0001) This application claims the benefit of U.S. Provi ^2. M sional Patent Application No. 60/314,978 filed Aug. 24, L-y CE c=y 2001 Attorney Docket No. CIT-3525-Pl; U.S. application X1. R Ser. No. 10/017,489 filed Dec. 14, 2001 Attorney Docket No. CIT-3525); U.S. application Ser. No. 10/107,531 filed Mar. 25, 2002 Attorney Docket No. CYM-120); U.S. 0005) wherein: application Ser. No. 10/138,188 filed May 3, 2002 Attorney 0006 M is ruthenium or osmium; Docket No. CYM-130; U.S. Provisional Application No. 0007 X and X’ are the same or different and are 60/309,806 filed Aug. 1, 2001 Attorney Docket No. CIT. each independently an anionic ligand; 3517 and, U.S. patent application Ser. No. 09/948,115, filed 0008) L, L'and L are the same or different and are Sep. 5, 2001 Attorney Docket No. CIT-3282, the contents each independently a neutral electron donor ligand; of each of which are incorporated herein by reference. and, 0002 The U.S. Government has certain rights in this 0009 R and R' are each independently hydrogen or invention pursuant to Grant No. CHE-9809856 awarded by a Substituent Selected from the group consisting of the National Science Foundation. C-Cao alkyl, Ca-Co alkenyl, Ca-Cao alkynyl, aryl, C-C20 carboxylate, C-C20 alkoxy, Ca-Coalkeny BACKGROUND loxy, C2-Co alkynyloxy, aryloxy, C2-Co alkoxycar bonyl, C-C alkylthio, C-C alkylsulfonyl, 0.003 Metathesis catalysts have been previously C-Cao alkylsulfinyl, and silyl. Optionally, each of described by for example, U.S. Pat. Nos. 5,312,940, 5,342, the R or R' substituent group may be substituted with 909, 5,728,917, 5,750,815, 5,710,298, and 5,831,108 and one or more moieties Selected from the group con PCT Publications WO 97/20865 and WO 97/291.35 which sisting of C-C alkyl, C-C alkoxy, and aryl which in turn may each be further substituted with are all incorporated herein by reference. These publications one or more groups Selected from a halogen, a C-Cs describe well-defined Single component ruthenium or alkyl, C-C alkoxy, and phenyl. Moreover, any of osmium catalysts that possess Several advantageous proper the catalyst ligands may further include one or more ties. For example, these catalysts are tolerant to a variety of functional groups. Examples of Suitable functional functional groups and generally are more active than previ groups include but are not limited to: hydroxyl, thiol, ously known metathesis catalysts. Recently, the inclusion of thioether, ketone, aldehyde, ester, ether, amine, an N-heterocyclic carbene (NHC) ligand, Such as an imida imine, amide, nitro, carboxylic acid, disulfide, car Zolidine or triazolylidene ligand as described in U.S. appli bonate, isocyanate, carbodiimide, carboalkoxy, car cation Ser. Nos. 09/539,840, 09/576,370 and PCT Publica bamate, halogen, alcohol, Sulfonic acid, phosphine, tion No. WO 99/51344, the contents of each of which are imide, acetal, ketal, boronate, cyano, cyanohydrin, incorporated herein by reference, in these metal-carbene hydrazine, enamine, Sulfone, Sulfide, and Sulfenyl. complexes has been found to improve the already advanta 0010. In preferred embodiments, L and L'are geous properties of these catalysts. In an unexpected and and L is a phosphine or an N-heterocyclic carbene ligand. Surprising result, the shift in Structure from the well-estab Examples of N-heterocyclic carbene ligands include: lished penta-coordinated catalyst Structure to the hexacoor dinated catalyst Structure has been found to significantly improve the properties of the catalyst. For example, these R6 R7 R6 R. R. R7 hexacoordinated catalysts of the present invention exhibit increased activity and Selectivity not only in ring closing metathesis (“RCM”) reactions, but also in other metathesis R10-N N-R11 R10-N N-R11 reactions including croSS metathesis (“CM’) reactions, reac N1 N1 tions of acyclic olefins, and ring opening metathesis poly OO OO merization (“ROMP”) reactions. R7 NS SUMMARY R- N-R 11 N1 0004. The present invention relates to novel hexacoordi nated metathesis catalysts and to methods for making and using the Same. The inventive catalysts are of the formula 0.011 wherein R, R R,R,R,R,R'' and R'' are each independently hydrogen or a Substituent Selected from the L R1 L R1 group consisting of C1-Co alkyl, C2-Co alkenyl, C2-Co ... / X. M alkynyl, aryl, C-Co carboxylate, C-Co alkoxy, C2-Co L1- W.V O L-C-Q O alkenyloxy, C-Co alkynyloxy, aryloxy, C-Co alkoxycar X'1. R X 1. R bonyl, C-C alkylthio, C-C alkylsulfonyl, C-C alkyl sulfinyl and silyl. Optionally, each of the R, R. R. R. R. US 2003/0069374A1 Apr. 10, 2003

R. R'' and R' substituent group may be substituted with one or more groups Selected from a halogen, a C-C alkyl, one or more moieties Selected from the group consisting of C-C alkoxy, and phenyl. Moreover, any of the catalyst C-Co alkyl, C-C alkoxy, and aryl which in turn may ligands may further include one or more functional groups. each be further Substituted with one or more groupS. Selected Examples of Suitable functional groups include but are not from a halogen, a C-C alkyl, C-C alkoxy, and phenyl. limited to: hydroxyl, thiol, thioether, ketone, aldehyde, ester, Moreover, any of the catalyst ligands may further include ether, amine, imine, amide, nitro, carboxylic acid, disulfide, one or more functional groups. Examples of Suitable func carbonate, isocyanate, carbodiimide, carboalkoxy, carbam tional groups include but are not limited to: hydroxyl, thiol, ate, halogen, alcohol, Sulfonic acid, phosphine, imide, thioether, ketone, aldehyde, ester, ether, amine, imine, acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyan enamine, Sulfone, Sulfide, and Sulfenyl. ate, carbodiimide, carboalkoxy, carbamate, halogen, alco hol, Sulfonic acid, phosphine, imide, acetal, ketal, boronate, 0019. The catalysts of the present invention are similar in cyano, cyanohydrin, hydrazine, enamine, Sulfone, Sulfide, that they are Ru or OS complexes; however, in these com and Sulfenyl. The inclusion of an NHC ligand to the hexa plexes, the metal is formally in the +2 oxidation State, and coordinated ruthenium or OSmium catalysts has been found has an electron count of 18 and are hexacoordinated. These to dramatically improve the properties of these complexes. catalysts are of the general formula: Because the NHC-based hexacoordinated complexes are extremely active, the amount of catalysts that is required is Significantly reduced. L R1 L-y... V/ DETAILED DESCRIPTION OF THE X'1. R PREFERRED EMBODIMENTS 0012. The present invention generally relates to ruthe nium and osmium carbene catalysts for use in olefin met 0020 wherein athesis reactions. More particularly, the present invention relates to hexacoordinated ruthenium and osmium carbene 0021 M is ruthenium or osmium; catalysts and to methods for making and using the Same. The 0022 X and X’ are the same or different and are terms “catalyst” and “complex' herein are used interchange each independently any anionic ligand; ably. 0023) L, L', and L are the same or different and are 0013 Unmodified ruthenium and osmium carbene com each independently any neutral electron donor plexes have been described in U.S. Pat. Nos. 5,312,940, ligand; 5,342,909, 5,728,917, 5,750,815, and 5,710,298, all of which are incorporated herein by reference. The ruthenium 0024 RandR are the same or different and are each and osmium carbene complexes disclosed in these patents independently hydrogen or a Substituent Selected all possess metal centers that are formally in the +2 oxida from the group consisting of C-Co alkyl, C-Co tion State, have an electron count of 16, and are penta alkenyl, C-Co alkynyl, aryl, C-Clo carboxylate, coordinated. These catalysts are of the general formula C-Co alkoxy, Co-Co alkenyloxy, Co-Co alkyny loxy, aryloxy, C-C alkoxycarbonyl, C-C alky lthio, C-C alkylsulfonyl, C-Co alkylsulfinyl, and L R1 silyl. Optionally, each of the R or R' substituent group may be Substituted with one or more moieties S Selected from the group consisting of C-Co alkyl, x1, \ C-Clo alkoxy, and aryl which in turn may each be further Substituted with one or more groups Selected from a halogen, a C-C alkyl, C-C alkoxy, and 0014) wherein: phenyl. Moreover, any of the catalyst ligands may further include one or more functional groups. 0.015 M is ruthenium or osmium; Examples of Suitable functional groups include but 0016 X and X’ are each independently any anionic are not limited to: hydroxyl, thiol, thioether, ketone, ligand; aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, car 0017 L and L are each independently any neutral bodiimide, carboalkoxy, carbamate, halogen, alco electron donor ligand; hol, Sulfonic acid, phosphine, imide, acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, enamine, 0018) R and R' are the same or different and are each Sulfone, Sulfide, and Sulfenyl. independently hydrogen or a Substituent Selected from the group consisting of C1-Co alkyl, C2-Co alkenyl, C2-Co 0025 The hexacoordinated complex provides several alkynyl, aryl, C-Clo carboxylate, C-Co alkoxy, C-Co advantages over the well-known pentacoordinated com alkenyloxy, Ca-Co alkynyloxy, aryloxy, C-Co alkoxycar plexes. For example, the hexacoordinated complexes have bonyl, C-C alkylthio, C-C alkylsulfonyl, C-C alkyl greater air Stability in the Solid State because they are sulfinyl, and silyl. Optionally, each of the R or R' substituent coordinatively saturated. Due to the lability of the additional group may be Substituted with one or more moieties Selected ligand, e.g. , the complexes initiate faster than the from the group consisting of C-C alkyl, C-C alkoxy, phosphine based pentacoordinated Species. Slow initiation and aryl which in turn may each be further substituted with means that only a Small amount of complex is actually US 2003/0069374A1 Apr. 10, 2003 catalystically active thereby wasting much of the added complex. With faster initiators, catalyst loading is lowered. Further, and without being bound by theory, it is believed that the slower propogation of the hexacoordinated com plexes, due to the re-binding of the labile ligands relative to the , translates to lower polydisperity. Moreover, the coordinatively Saturated Species crystallize better than their pentacoordinated counterparts. In addition, due to the lability of the ligands in the hexacoordinated complexes (e.g. pyridines and chlorines), these complexes allow access 0028 wherein M, L, L', L', L, X, X', and R are as to previously inaccessible complexes and provide with defined above. R' and R" are preferably independently higher purity certain complexes that can be obtained through hydrogen or phenyl but can be Selected from any of the different routes. For example, the pentacoordinated ben groups listed for R or R. Zylidene with triphenylphosphine as its phosphine ligand can be prepared in higher yield and with greater purity using 0029. In preferred embodiments of the inventive cata the hexacoordinated complex. The pentacoordinated ben lysts, X and X’ are each independently hydrogen, halide, or Zylidene with P(p-CFCH) as its phosphine ligand is one of the following groups: C-C alkyl, aryl, C-Co inaccessible through existing routes. Without being bound alkoxide, aryloxide, C-C alkyldiketonate, aryldiketonate, by theory, it is believe that this is because it would require C-C carboxylate, arylsulfonate, C-C alkylsulfonate, the Substitution of a stronger donor ligand with a weaker C-Cao alkylthio, C-Co alkylsulfonyl, or C-Co alkylsulfi donor ligand. Substitution of the anionic ligands of the nyl. Optionally, X and XI may be substituted with one or hexacoordinated complexes is much more rapid than with more moieties Selected from the group consisting of C-Co the corresponding pentacoordinated species (e.g. phosphine alkyl, C-C alkoxy, and aryl which in turn may each be bound). Without being bound by theory, it is believed that further Substituted with one or more groups Selected from this results from the requirement of ligand dissociation halogen, C-C alkyl, C-C alkoxy, and phenyl. In more before anionic ligand Substitution. Thus complexes with fast preferred embodiments, X and X’ are halide, benzoate, dissociation of their neutral electron donor ligands will C-C carboxylate, C-C alkyl, phenoxy, C-C alkoxy, undergo faster Substitution. C-Cs alkylthio, aryl, and C1-C5 alkyl sulfonate. In even 0026. The catalysts of the invention are also useful for more preferred embodiments, X and X’ are each halide, ring-opening metathesis polymerization (ROMP), ring-clos CFCO, CHCO, CFHCO, (CH) CO, (CF) (CH)CO, ing metathesis (RCM), ADMET, and cross-metathesis. The (CF)(CH3)2CO, PhO, MeO, EtO, tosylate, mesylate, or Synthesis and polymerization of olefins via these metathesis trifluoromethanesulfonate. In the most preferred embodi reactions can be found in, for example, U.S. application Ser. ments, X and X’ are each chloride. No. 09/891,144 entitled: “Synthesis of Functionalized and 003.0 L, L', L'and Lf may be any appropriate monoden Unftinctionalized Olefins, filed Jun. 25, 2001, and U.S. tate or multidentate neutral electron donor ligands. Multi application Ser. No. 09/491,800, the contents of each of dentate neutral electron donor ligands include bidentate, which are incorporated herein by reference. Preferred tridentate, or tetradentate neutral electron donor ligands, for embodiments of the catalysts of the invention possess at example. In preferred embodiments of the inventive cata least one NHC ligand attached to the metal center, as lysts, L., L', L'and L are each independently selected from illustrated by the following general formula: the group consisting of phosphine, Sulfonated phosphine, phosphite, , phosphonite, arsine, Stibine, ether, NHC R1 amine, amide, imine, , carboxyl, nitrosyl, pyridine, a / and thioether, or any derivatives therefrom. At least one L, L1- W.V L', L'and Li may also be an N-heterocyclic carbene ligand. X'1. R Preferred embodiments include complexes where both L' and L are either the same or different NHC ligands. 0027. In preferred embodiments of the inventive cata 0031) In preferred embodiments, at least one of L, L', lysts, the R substituent is hydrogen and the R' substituent is Land L is a phosphine of the formula PRRR, where R, Selected from the group consisting of C-C alkyl, C-Co R", and R are each independently aryl or C-Clio alkyl, alkenyl, and aryl. In even more preferred embodiments, the particularly primary alkyl, Secondary alkyl or cycloalkyl. In R" substituent is phenyl or vinyl, optionally substituted with the even more preferred embodiments, at least one of L, L', one or more moieties Selected from the group consisting of L'and Li is each selected from the group consisting of C-C alkyl, C-C alkoxy, phenyl, and a . -P(cyclohexyl)-, -P(cyclopentyl), -P(isopropyl), and In especially preferred embodiments, R is phenyl or vinyl -P(phenyl)s. Even more preferably, at least one of L, L', Substituted with one or more moieties selected from the L'and L is an NHC ligand. A preferred embodiment group consisting of chloride, bromide, iodide, fluoride, include where L is an NHC, L' is P(cyclohexyl) or -P(cy -NO, -NMe2, methyl, methoxy and phenyl. In the most clopentyl)s, and L'and L are each heterocyclic ligands, preferred embodiments, the R' substituent is phenyl or optionally aromatic, or together form a bidenatate ligand. -C=C(CH). When R is vinyl, the catalyst is of the Preferably Land L are each independently pyridine or a general formula: pyridine derivative. US 2003/0069374A1 Apr. 10, 2003

0.032 Examples of NHC ligands include ligands of the thermal stability. In especially preferred embodiments, R' general formulas: and R'' are the same and each is independently of the formula:

R6 R7 R6 R. R. R7 R12

R10-N N-R11 R10-N N-R11 N/ N1 OO OO R7 N R- N-R 11 N1 0036) wherein: 0037) R', R', and R'' are each independently hydrogen, C-Co alkyl, C-Co alkoxy, aryl, or a functional group Selected from hydroxyl, thiol, thio 0033 wherein R, R, R', R", R, R7, R. R. R', and R' ether, ketone, aldehyde, ester, ether, amine, imine, are each independently hydrogen or a Substituent Selected amide, nitro, carboxylic acid, disulfide, carbonate, from the group consisting of C-C alkyl, C-C alkenyl, isocyanate, carbodiimide, carboalkoxy, carbamate, C-Co alkynyl, aryl, C-Co carboxylate, C-Co alkoxy, and halogen. In especially preferred embodiments, C-Cao alkenyloxy, Ca-Cao alkynyloxy, aryloxy, Ca-Cao R', R', and R'' are each independently selected alkoxycarbonyl, C-C alkylthio, C-C alkylsulfonyl, from the group consisting of hydrogen, methyl, C-C alkylsulfinyl, and silyl. Optionally, each of the R, R' ethyl, propyl, isopropyl, hydroxyl, and halogen. In R*, R7, R, R, R', and R' substituent group may be the most preferred embodiments, R', R', and R' Substituted with one or more moieties selected from the are the Same and are each methyl. group consisting of C-Clio alkyl, C-Clio alkoxy, and aryl 0.038. In these complexes, R, R, R, and R are each which in turn may each be further substituted with one or independently hydrogen or a Substituent Selected from the more groups Selected from a halogen, a C-C alkyl, C-Cs group consisting of C1-Co alkyl, C2-Co alkenyl, Co-Co alkoxy, and phenyl. Moreover, any of the catalyst ligands alkynyl, aryl, C-Clo carboxylate, C-Co alkoxy, C-Co may further include one or more functional groups. alkenyloxy, Ca-Co alkynyloxy, aryloxy, C2-Co alkoxycar Examples of Suitable functional groups include but are not bonyl, C-C alkylthio, C-C alkylsulfonyl and C-Co limited to: hydroxyl, thiol, thioether, ketone, aldehyde, ester, alkylsulfinyl. Imidazolidine ligands are also referred to as ether, amine, imine, amide, nitro, carboxylic acid, disulfide, imidizol-2-ylidene ligands. carbonate, isocyanate, carbodiimide, carboalkoxy, carbam ate, halogen, alcohol, Sulfonic acid, phosphine, imide, 0039) Other examples of neutral electron donor ligands acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, include ligands which are derived, for example, from unsub enamine, Sulfone, Sulfide, and Sulfenyl. Stituted or Substituted heteroarenes Such as furan, thiophene, pyrrole, pyridine, bipyridine, picolylimine, gamma-pyran, 0034). In preferred embodiments, R, R, R and R are gamma-thiopyran, phenanthroline, pyrimidine, bipyrimi independently Selected from the group consisting of hydro dine, pyrazine, indole, coumarone, thionaphthene, carba gen, phenyl, or together form a cycloalkyl or an aryl Zole, dibenzofuran, dibenzothiophene, pyrazole, imidazole, optionally Substituted with one or more moieties Selected benzimidazole, oxazole, thiazole, dithiazole, isoxazole, from the group consisting of C-Coalkyl, C-Coalkoxy, isothiazole, quinoline, bisquinoline, isoquinoline, bisiso aryl, and a functional group Selected from the group con quinoline, acridine, chromene, phenazine, phenoxazine, Sisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, phenothiazine, triazine, thianthrene, purine, bisimidazole ether, amine, imine, amide, nitro, carboxylic acid, disulfide, and bisoxazole. carbonate, isocyanate, carbodiimide, carboalkoxy, carbam ate, and halogen; and R'' and R' are each is independently 0040 Examples of substituents are OH, halogen, C-Co alkyl or aryl optionally Substituted with C-C alkyl, C(O)OR1, OC(O)R., C(O)R., nitro, NH, cyano, SOM, C-C alkoxy, aryl, and a functional group Selected from the OSOM, NROSOM, N=N-R, C-C alkyl, C-C, group consisting of hydroxyl, thiol, thioether, ketone, alde alkenyl, C-C alkoxy, C-C cycloalkyl, C-C cycloalk hyde, ester, ether, amine, imine, amide, nitro, carboxylic enyl, C-C heterocycloalkyl, C-C heterocycloalkenyl, acid, disulfide, carbonate, isocyanate, carbodiimide, car C-Clo aryl, Co-Cio aryloxy, Cs-Coheteroaryl, Cs-Co het boalkoxy, carbamate, halogen, alcohol, Sulfonic acid, phoS eroaryloxy, C7-Caralkyl, C7-Caralkyloxy, Co-Co het phine, imide, acetal, ketal, boronate, cyano, cyanohydrin, eroaralkyl, C-C aralkenyl, C7-Co heteroaralkenyl, hydrazine, enamine, Sulfone, Sulfide, and Sulfenyl. monoamino, diamino, Sulfonyl, Sulfonamide, carbamide, carbamate, Sulfohydrazide, carbohydrazide, carbohydrox 0035) In more preferred embodiments, Rand R7 are both amic acid residue and aminocarbonylamide, in which R is hydrogen or phenyl, or RandR together form a cycloalkyl hydrogen, My, C1-C12 alkyl, C-C2 alkenyl, C-C2 group; R and R are hydrogen and R' and R'' are each cycloalkyl, C-C heterocycloalkyl, Co-Co aryl, Cs-Co het either substituted or unsubstituted aryl. Without being bound eroaryl, C7-C aralkyl or Co-Co heteroaralkyl, R is by theory, it is believed that bulkier R'' and R' groups hydrogen, C-C2 alkyl, C2-C2 alkenyl, C-C2 cycloalkyl, result in catalysts with improved characteristics Such as C-C heterocycloalkyl, Co-Co aryl, Cs-Co heteroaryl, US 2003/0069374A1 Apr. 10, 2003

C7-Caralkyl or Co-Co heteroaralkyl, and R2 and Rao are I and Z is a monovalent metal or y is /2 and Z is a divalent hydrogen, C-C2 alkyl, C2-C2 alkenyl, C-C2 cycloalkyl, metal; or Rs and R or Rand Roor Rs and Rao in the case C-C cycloalkenyl, C-C heterocycloalkyl, C-C het of -NRRo or -NRRo, or RRoN- together are tet erocycloalkenyl, Co-Co aryl, Cs-Co heteroaryl, C7-C ramethylene, pentamethylene, -(CH2)-O-(CH2) , aralkyl, Co-Co heteroaralkyl, C-C aralkenyl or C7-Co heteroaralkenyl, and alkyl, alkenyl, alkoxy, cycloalkyl, (CH-)-S-(CH)-or (CH)-NR,-(CH), cycloalkenyl, heterocycloalkyl, heterocycloalkenyl, aryl, and R7 is H, C-C alkyl, C7-Caralkyl, C(O)R or Sulfo aryloxy, heteroaryl, heteroaryloxy, aralkyl, aralkyloxy, het nyl. eroaralkyl, aralkenyl and heteroaralkenyl in turn are unsub 0042. The sulfonyl substituent is, for example, of the stituted or substituted by one of the above-mentioned sub formula Ro-SO2- in which Ro is C-C alkyl, C-C2 Stituents, and y is 1 and M is a monovalent metal or y is /2 cycloalkyl, C-C heterocycloalkyl, Co-Co aryl, Cs-Co het and M is a divalent metal. eroaryl, C7-Caralkyl or C-C heteroaralkyl which are 0041. In the context of the description of the present unsubstituted or substituted by one or more substituents invention, the terms metal and corresponding cations refer to Selected from the group consisting of OH, halogen, an alkali metal, for example Li, Na or K, an alkaline earth C(O)OR1, OC(O)R., C(O)R., nitro, NH, cyano, SOZ, metal, for example Mg, Ca or Sr., or Mn, Fe, Zn or Ag, and OSO-Z, NROSO-Z, Ca-Cia alkyl, Ca-Cia alkenyl, C-C2 corresponding cations. Lithium, Sodium and potassium ions, alkoxy, C-C2 cycloalkyl, C-C2 cycloalkenyl, C2-C. het with their Salts, are preferred. NH, monoamino, diamino, erocycloalkyl, C-C heterocycloalkenyl, C-C aryl, carbamide, carbamate, carbohydrazide, Sulfonamide, Sulfo C-Clo aryloxy, Cs-Co heteroaryl, Cs-Co heteroaryloxy, hydrazide and aminocarbonylamide correspond preferably C-C, aralkyl, Co-Co heteroaralkyl, Cs-C, aralkenyl, to a group Rs C(O)(NH)N(R)-, -C(O)(NH), NRs.R., C-Co heteroaralkenyl, monoamino, diamino, Sulfonyl, Sul R.OC(O)(NH),N(R)-, R.R.ONC(O)(NH), N(R)-, fonamide, carbamide, carbamate, Sulfonhydrazide, carbohy -OC(O)(NH), NRs.R., -N (Rio)C(O)(NH),NRRo, drazide, carbohydroxamic acid residue and aminocarbony RS(O) (NH) pN(R)-, -S(O) 2 (NH),NR8Re; lamide, in which R, is hydrogen, Z, C-Clalkyl, R.RONS(O)N(R)-or -NROS(O)NR,R, in which C2-C2alkenyl, C-C2 cycloalkyl, C2-C. heterocycloalkyl, Rs, Ro and Rio independently of one another are hydrogen, OH, C-C alkyl, C-C alkenyl, C-C cycloalkyl, Co-Co aryl, Cs-Co heteroaryl, C7-C aralkyl or Co-Co C-C2 cycloalkenyl, Ca-C, heterocycloalkyl, C-C, het heteroaralkyl, R is hydrogen, C-C alkyl, C-C alkenyl, erocycloalkenyl, Co-Co aryl, Cs-Co heteroaryl, C7-Co C-C2 cycloalkyl, C-C heterocycloalkyl, Co-Co aryl, aralkyl, Cs-Caralkenyl With C-Calkenylene and Co-Co C-Co heteroaryl, C7-C, aralkyl or Co-Co heteroaralkyl, aryl, Co-Cls heteroaralkyl, Co-Cls heteroaralkenyl, or di-C- and R2 and Ro are hydrogen, C-C alkyl, C-C alkenyl, Co aryl-C-C alkyl, or RsRN, in which Rand C-C2 cycloalkyl, C-C2 cycloalkenyl, C2-C. heterocy Roindependently of one another are hydrogen, OH, SOM, cloalkyl, C-C heterocycloalkenyl, C-Caryl, Cs-Co het OSOM, C-C2 alkyl, C-C cycloalkyl, C-C, hetero eroaryl, C7-Caralkyl, Co-Co heteroaralkyl, Cs-Caralk cycloalkyl, Co-Co aryl, Cs-Co heteroaryl, C7-Caralkyl, enyl or C7-Co heteroaralkenyl, and alkyl, alkenyl, alkoxy, C-Co heteroaralkyl, Cs-Co aralkenyl with C-C alk cycloalkyl, cycloalkenyl, heterocycloalkyl, heterocycloalk enylene and C-C aryl, or di-C-C aryl-C-C alkyl, enyl, aryl, aryloxy, heteroaryl, heteroaryloxy, aralkyl, het which are unsubstituted or substituted by one or more eroaralkyl, aralkenyl and heteroaralkenyl in turn are unsub Substituents from the group consisting of OH, halogen, stituted or substituted by one of the above-mentioned C(O)OR1, OC(O)R., C(O)R., nitro, NH, cyano, SOZ, Substituents, and y is 1 and Z is a monovalent metal or y is OSO-Z, NRoSO-Z, C-C alkyl, C-C2 alkenyl, C-C2 % and Z is a divalent metal. Preferred neutral electron donor alkoxy, C-C2 cycloalkyl, C-C2 cycloalkenyl, C2-C. het ligands are derived, for example, from heteroarenes of the erocycloalkyl, C-C heterocycloalkenyl, Co-Co aryl, group C-Caryloxy, Cs-C heteroaryl, Cs-C heteroaryloxy, C-C, aralkyl, C7-C, aralkyloxy, Co-Co heteroaralkyl, C-C, aralkenyl, C, -Co heteroaralkenyl, monoamino, N O N N CHO diamino, Sulfonyl, Sulfonamide, carbamide, carbamate, Sul n h 2 2 fohydrazide, carbohydrazide, carbohydroxamic acid residue and aminocarbonylamide, in which R is hydrogen, Zy 21 N 'N N C-C12 alkyl, C-C2 alkenyl, Ca-C12 cycloalkyl, C-C, heterocycloalkyl, C-C aryl, Cs-Co heteroaryl, C7-C CH CH N(CH3)2 aralkyl or Co-Co heteroaralkyl, R is hydrogen, C-C2 alkyl, C-C alkenyl, C-C cycloalkyl, C-C heterocy cloalkyl, Co-Co aryl, Cs-Co heteroaryl, C7-Caralkyl or C-Co heteroaralkyl, and R2 is hydrogen, C-C2 alkyl, N N O C-C2 alkenyl, C5-C12 cycloalkyl, Ca-C12 cycloalkenyl, C-C, heterocycloalkyl, C-C, heterocycloalkenyl, HC CH l) X Co-Coaryl, Cs-Co heteroaryl, C7-Caralkyl, Co-Co het eroaralkyl, Cs-Caralkenyl or C7-Co heteroaralkenyl, and N21 21 NN alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, heterocy cloalkyl, heterocycloalkenyl, aryl, aryloxy, heteroaryl, het N 21 N 2^ eroaryloxy, aralkyl, aralkyloxy, heteroaralkyl, aralkenyl and heteroaralkenyl in turn are unsubstituted or substituted by N-N S one of the above-mentioned Substituents; p is 0 or I and y is US 2003/0069374A1 Apr. 10, 2003

-continued -continued

21 N 21 NN

N

rol CH C(CH3)3 21 NN S 2N N NO2 21 NN CH

N l in rol N 21 | N S.

CN NO 21 NN

-- c. N(CH3)2 21 NN N 2N

N | N

N(CH3)2

0043. A more preferred group of compounds is formed when L and L'independently of one another are pyridyl which is unsubstituted or substituted by one or more sub Stituents from the group consisting of C-C alkyl, C-C, heterocycloalkyl, Cs-Co heteroaryl, halogen, monoamino, diamino and -C(O)H. Examples are OOl 2's COCCH C) US 2003/0069374A1 Apr. 10, 2003 7

-continued -continued 2^ CHO e. N 21 N / V 1 N N 21 NN N N Br N W( y\ (/ D S 2 Na S S CH(CH3)2

r 2 N N 21 -1 t 21 -1 21 J - N 4-Yet, N 2 N NO

21 1 | J - 0044 Another preferred group of compounds is formed N 2 when L and L'together are bipyridyl, phenanthrolinyl, bithiazolyl, bipyrimidinyl or picolylimine which are unsub- CH stituted or substituted by one or more substituents from the group consisting of C-C2 alkyl, Co-Co aryland cyano, the 21 -1 | Substituents alkyl and aryl being in turn unsubstituted or Substituted by one or more Substituents from the group N 2N consisting of C-C alkyl, nitro, monoamino, diamino and nitro- or diamino-substituted -N=.N-C-C aryl. Examples are: |

US 2003/0069374A1 Apr. 10, 2003

carboxylate, C-C20 alkoxy, C2-Co alkenyloxy, C2-Co -continued alkynyloxy, aryloxy, C-C alkoxycarbonyl, C-C alky lthio, C-C alkylsulfonyl, C-Co alkylsulfinyl, and silyl. 21 1. Optionally, the R group may be Substituted with one or more moieties Selected from the group consisting of C-Co alkyl, N 2 N C-C alkoxy, and aryl which in turn may each be further Substituted with one or more groups Selected from a halogen, N a C-C alkyl, C-C alkoxy, and phenyl. Moreover, any of | the heterocycles may further include one or more functional N groups. Examples of Suitable functional groups include but are not limited to: hydroxyl, thiol, thioether, ketone, alde hyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, car boalkoxy, carbamate, halogen, alcohol, Sulfonic acid, phos 0045) Even more preferably, Land L'are each indepen phine, imide, acetal, ketal, boronate, cyano, cyanohydrin, dently Selected from the group consisting of: hydrazine, enamine, Sulfone, Sulfide, and Sulfenyl. Prefer ably R is selected from the group consisting of C-C alkyl, aryl, ether, amine, halide, nitro, ester and pyridyl. 0047 Preferably complexes 1-4 and 44-48 are used to make the preferred embodiments 5-29 and 49-83 of the OCOCO inventive complex: OCCO (, , ,

CO)CC

OCH3

N N N N N R OOOOO2 2 21 21 21 Br NO ot

0.046 wherein R is selected from the group consisting of hydrogen or a Substituent Selected from the group consisting of C1-Coalkyl, Ca-Coalkenyl, C-Coalkynyl, aryl, C.-Co US 2003/0069374A1 Apr. 10, 2003

-continued -continued 12 SIMES V Cl 12, —VCl Ms Br n N-Ru 21 Br

SIMES rsr.21 N N-Ru \ / w Cl Ph 13 n - VCl Ms \ isCl Ph n 21

14

15

16

17 11 / Y, US 2003/0069374A1 Apr. 10, 2003 10

-continued -continued 18 PCp3 24 - V. Cl . -O — Cn

19

25

26 21

27 SIMES 22

/ \ A S\{N \ /Sn (

23 28 - VC. \ /N-Ru NW N o n

US 2003/0069374A1 Apr. 10, 2003 15

-continued -continued NHC R NHC R X. / X. M 2b X1 Y. X1 Y. C D RECECECfe 13 13 C11 X. , X2, R PCp3

MSC-QX 1. R1 st-c=QX 1. R1 3a

C 0051 wherein M and M' are independently selected from D Ruo CFC the group consisting of ruthenium and osmium, X, X', L, C11 L', R and R' are as previously defined, X and X'are PCys Substituted or unsubstituted and are independently Selected from the group from which X and X’ are selected, R' and Rare substituted or unsubstituted and are independently selected from the group from which R and R' are selected, 3b L'is selected from the group from which L'is selected, L’is C fy any bidentate, neutral electron donor ligand, and L is any > Ru-C=C= tetradentate, neutral electron donor ligand. C11 0.052 The carbene complexes of the invention may also PCys be cumulated. For example, one aspect of the invention is a catalyst of the general Structure: 4a

L R L R N N X2. M X. M

L1 C=1. O L'-y' 1. =C= X R1 X R1 D RuCFC c1 | PCys 0053 wherein M, L,L,L,L, X, X', R and R' are as defined above. In Such cases, the Starting complexes may be 4b selected from the following:

1a N N

c1 RFCFCFC PCys

0054 Using cumulated pentacoordinated complexes, for 1b example, those seen in complexes 1-4 (a,b), in the inventive process will produce inventive cumulated hexacoordinated complexes. For example, the cumulated complexes corre sponding to complex 5 is as follows:

5a

2a US 2003/0069374A1 Apr. 10, 2003

0064. The synthesis of a preferred embodiment is shown -continued in Scheme 2: Sb

sImes SCHEME 2

SIMES SIMES Cl Ph Cl Ph 2. M excess pyridine / \ 2. Ru v -R v |Y. H o |Y. H PCys N 21 0.055 Similarly, compounds 6-29 may also have corre N sponding cumulated complexes. O 0056. In all of the above carbene complexes, at least one Ph Ph of L, L', L', Li, X, X', R and R', may be linked to at least Cl SIMES /-( CXCeSS C SIMES =( one other of L, L', L', Li, X, X', R and R' to form a 2. pyridine / \ 2. bidentate or multidentate ligand array. RFCH H He- N-RuCH H PCys|Y, =/ NY, 0057) Synthesis: 21 0.058. In general, the inventive catalysts are made by contacting exceSS neutral electron donor ligand, Such as a N pyridine, with the previously described penta-coordinated metal carbene catalyst complex of the formula: 0065. As shown by Schemes 1 and 2, in the presence of excess ligand L, the pentacoordinated complex loses the L' X R1 ligand and ligands L and L'attach to the metal center. \ / MC Ligands L and L'may be the same compound, for example, A V pyridines (when excess pyridine is used), or may together X 1 R form a bidentate ligand. Alternatively, L' and L'may be the Same, in which case, the pentacoordinated compound does not necessarily lose the L' ligand in the presence of excess 0059) wherein: L2. 0060 M, X, X', L, L', R and R' are as previously 0066. The inventive complex may also be a cumulated defined; and carbene complex of the general formulas: 0061 wherein the third neutral electron donor ligand attaches to the metal center. Scheme 1 shows the general L R L R Synthesis reaction for forming the inventive hexacoordi X. M Xz. M nated metal carbene complexes: L'-y' 1. =c, O L-C-C=c,1. X R1 X R1

SCHEME 1 0067 wherein M, X, X', L, L', L', L, R and R' are as X2. MR excess L’ 1. X2. MR MC Ho- Li-MC previously defined. The Synthesis of these compounds W . \ W . \ would follow Scheme 1 except that the Starting compound X1 R1 X1 R1 would be a pentacoordinated Vinylidene or pentacoordinated L1 2 , respectively. The Synthesis of preferred embodi O ments of the vinylidenes can be seen in Scheme 3: R R

SCHEME3 X1. . /-( excess L’ X1. . /-( MCH R1 -as- L1-MECH R1 PC X1 X1 C \ PCy3 A H pyridineexcess =VC-- 8 A H RuCC Her \ N-RECC CH L1 2 / V -CH3 Y 3 Cl PCys iSch N NCH, 3 S CH CH 0062 wherein: 2 0063 M, X, X', L, L', L', L, R and R' are as O previously defined. US 2003/0069374A1 Apr. 10, 2003 17

-continued C PCy3 H excess r C1 PCys H SCHEME 4 w A pyridine 2. M Ru CFC --- N-RuCC / V / X1. , -L2 N ,' C PC C L1 FCEC s MECFC y3 N W V -L2 A V S X1 R X1 R 2 2 L1'

0068. Other preferred compounds synthesized by the 0071. The pentacoordinated complex may also lose the inventive method include where L and L'form a bidentate L ligand to form the metathesis active tetracoordinated ligand: Species (Scheme 5):

SCHEME5

and N R' -L1. N ?' MECEC SS MECEC A V --L A V X1 R X1 R L1

0072) As shown in Scheme 5, the L' ligand may also attach to a tetracoordinated Species to form the pentacoor dinated complex. 0073. The tetracoordinated species may then initiate polymerization when in the presence of an olefin, as shown in Scheme 6, or may form the NHC-ligand based pentaco ordinated complex when in the presence of a protected NHC-ligand (Scheme 7): 0069. The inventive hexacoordinated catalyst complexes provide Synthetic utility and utility in catalytic reactions. SCHEME 6 -- Without being bound by theory, these complexes contain X R1 V X R1 Substitutionally labile ligands, for example, pyridine and V M R. \ M chloride ligands, and Serve as a versatile Starting material for M=C=c, -- =C=Q X1 R V X1 R the Synthesis of new ruthenium metal carbene complexes. Ry The chloride ligands are more labile than in the correspond ing pentacoordinated phosphine-based complexes. AS Stated Ry above, X and X’ are any anionic ligand. Preferably X and X' are Selected from the group consisting of chloride, bromide, iodide, Tp, alkoxide, amide, and thiolate. The pyridine SCHEME 7 ligands are more labile than the phosphines in the corre sponding pentacoordinated phosphine-based complexes. -- R8 R9 Again, as stated above, L, L', L', and Lf can be any neutral X R1 R10-N N-R11 6 7 electron donor ligands, including a NHC ligand. Depending \ M Y1 R R on the size of the ligand, one or two neutral ligands (in M=C=c, S R10-N N-R11 addition to the NHC) may bind to the metal center. X1 R X R1 R6 R7 V M 0070 Interestingly, the inventive catalyst complexes may R10-N, N-R 11 == be used in both metathesis reactions or the formation of an N1 X R NHC ligand based complex. As shown in Scheme 4, the hexacoordinated complex can lose a neutral electron donor ligand to produce the pentacoordinated catalyst complex. 0074 The following structure NHC-A-B indicates gen The reaction may also proceed the other way to produce a erally the protected form of a N-Heterocyclic Carbene hexacoordinated complex in the presence of excess Lif. (NHC). US 2003/0069374A1 Apr. 10, 2003 18

0077. The NHC ligand based pentacoordinated complex may then lose the L ligand to form the metathesis active R11 tetracoordinated Species and proceed to initiate the polymer ization reaction in the presence of an olefin (Scheme 8): R.9 N R . A R8 X. SCHEME 8 R6 N l R8 R9 R8 R9 R-J - -L R-J - 0075). It is also envisioned that the protected NHC-A-B R10-N N-R11 SES R10-N N-R 11 may be of an unsaturated variety, Such as +L NYV MR1 NYV MR1 R11 MFCFC MFCFC / V A R. l X R X1 R

X. - RV + FV R6 OX,N l Ry Ry R8 R9 0.076. In the above structures, A is preferably H, Si, Sn, Li, Na, MgX and acyl, wherein X is any halogen, and B may be selected from the group consisting of CC1, R10-N N-R 11 X R1 CHSOPh; CF; OR; and N(R’)(R), wherein R is V M Selected from the group consisting of Me, CH5, i-CH7, MECEC CHCMe, CMe, CH, 1(cyclohexyl), CHPh, A V CH-norbornyl, CH-norbornenyl, CH5, 2,4,6-(CH-)-CH X1 R (mesityl), 2,6-i-PrCH, 4-Me-CH (tolyl), 4-C-CH, and wherein R* and Rare independently selected from the Ry group consisting of Me, CH5, i-CH7, CHCMes, CMes, CH, (cyclohexyl), CHPh, CH-norbornyl, CH-norbornenyl, CH5, 2,4,6-(CH-)-CH (mesityl), 2,6-i- 0078. It should also be noted that the hexacoordinated PrCH, 4-Me-CH (tolyl), 4-C-CH4). This approach complex can undergo a ligand exchange Such that the NHC relates to the thermal generation of a NHC ligand from a replaces another neutral electron donor ligand resulting in an stable (protected) NHC derivative with a release of a quan NHC ligand based hexacoordinated complex (Scheme 9): tity of A-B. One of the more preferred methods to generate a reactive NHC ligand is to employ a stable carbene pre cursor where the A-B compound is also a reactive NHC SCHEME 9 ligand. A detailed description of the protected NHC and R8 R9 related methods of Synthesis and use can be seen in U.S. * 6 patent application Ser. Nos. 10/107,531 and 10/138,188 the R R7 R8 R9 contents of each of which are incorporated herein by refer * L * R10-NN1 N-R 11 -L R6 R7 ence. The following structure for the sImesHCCls shows a L1-M=C=C R10-N, N-R11 preferred embodiment of a protected NHC ligand for use Y. V R8 R9 with the inventive hexacoordinated complexes: X R - 6 X R1 2 R10-NR-J N-R11-R, (+L LI-MECEC1. 3.--/ n-1 f Y \ X R 2

0079. In aall theC ab OVC, SCCCSh Cd COOCXCSpl M.s X.1 as X s L,L,L,L,R,R,R,R,R,R,R,R'', and R are as previously defined. 0080. The reaction of complex 1 with a large excess (~100 equiv) of pyridine results in a rapid color change from red to bright green, and transfer of the resulting Solution to cold (-10° C.) pentane leads to the precipitation of the bis-pyridine adduct (ImesH)(Cl) (CHN)Ru=CHPh (31). Complex 31 can be purified by several washes with pentane and is isolated as an air-stable green Solid that is soluble in CHCl, and THF. This procedure pro vides complex 31 in 80-85% yield and is easily carried out on a multigram Scale. US 2003/0069374A1 Apr. 10, 2003

0.081 Crystals suitable for X-ray crystal structure deter carbon) bond length of 1.873(4) A is slightly longer than mination were grown by vapor diffusion of pentane into a those in five-coordinate ruthenium olefin metathesis cata Saturated benzene Solution of 31 at room temperature. The lysts, including (Cl)(PCy)Ru=CHPh d(Ru==C)= collection and refinement parameters for the crystallo 1838(2) A) and complex 1 d(Ru=C)=1.835(2) A). Th graphic analysis are Summarized in Table 1. elongated Ru=C bond in 31 likely results from the pres ence of a trans pyridine ligand. The Ru--C(38) (N-hetero TABLE 1. cyclic carbene) bond length of 2.033(4) A is approximately 0.05 A shorter than that in complex 1, which is likely due to Crystal Data and Structure Refinement for Complex 31 the relatively Small size and moderate trans influence of Empirical formula Cze.HeClNRu pyridine relative to PCys. The 0.15 A difference in the Formula weight 1453.46 Ru-C(1) and Ru-C(38) bond distances highlights the Crystal habit Rod covalent nature of the former and the dative nature of the Crystal size 0.41 x 0.11 x 0.07 mm Crystal color Emerald green latter ruthenium-carbene bond. Interestingly, the two Ru-N Diffractometer CCD area detector bond distances differ by more than 0.15 A, indicating that Wavelength O.71073 Mo Koi. the benzylidene ligand exerts a significantly larger trans Temperature 98 K. influence than the N-heterocyclic carbene. Unit Cell Dimensions a = 12.3873(16) A b = 15.529(2) A 0084. The kinetics of the reaction between complex 1 and c = 18.562(2) A C = 78.475(2) pyridine was investigated in order to determine the mecha B = 81.564(2) nism of this ligand Substitution. The reaction of complex 1 y = 76.745(2) (0.88 M in toluene) with an excess of pyridine-ds (0.18-0.69 Volume 3386.2(8) A M) is accompanied by a 150 nm red shift visible MLCT Z. 4 Crystal system Triclinic absorbance, and this transformation can be followed by Space group P1 UV-vis SpectroScopy. The disappearance of Starting material Density (calculated) 2.758 Mg/m (502 nm) was monitored at 20° C., and in all cases, the data 0 range 1.61-28.51 fit first-order kinetics over five half-lives. A plot of kob, h min, max -16, 16 k min, max -20, 20 versus C5D5N is presented in FIG. 2. The data show an 1 min, max -24, 24 excellent linear fit (R-0.999) even at high concentrations of Reflections collected 76469 pyridine, and the y-intercept of this line (1.1x10) is very Independent reflections 15655 close to Zero. The rate constant for phosphine dissociation GOF on F2 1.438 RInt O.867 (k) in complex 1 has been determined independently by P Final R indices II > 2o (I) O.O609 magnetization transfer experiments, and at 20° C., kt is Final weighted R (F) 0.0855 4.1x10 S. This value of k places an upper limit on the rate of dissociative ligand exchange in 1, and the observed rate constants for pyridine Substitution are clearly 3 orders of 0082) A labeled view of complex 31 is shown in FIG. 1 magnitude larger than k. Taken together, these results and representative bond lengths and bond angles are indicate that the substitution of PCy with pyridine proceeds reported in Table 2: by an associative mechanism with a Second-order rate constant of 5.7x10° M's at 20° C. In marked contrast, TABLE 2 displacement of the phosphine ligand of 1 with olefinic Substrates (which is the initiation event in olefin metathesis Selected Bond Lengths (A) and Angles (deg) for Complex 31 reactions) occurs via a dissociative mechanism. Bond Lengths (A) 0085. Initial reactivity studies of complex 31 revealed Ru-C(1) 1.873(4) that both pyridine ligands are substitutionally labile. For Ru-N(3) 2.203(3) example, benzylidene 31 reacts instantaneously with 1.1 Ru-Cl(1) 2.3995(12) equiv. of PCys to release pyridine and regenerate complex 1. Ru-C(38) 2.033(4) Ru-N(4) 2.372(4) This equilibrium can be driven back toward the pyridine Ru-Cl(2) 2.4227(12) adduct by addition of an excess of CDN, but it is readily Bond Angles (deg) reestablished by removal of the volatiles under vacuum. C(38)-Ru-C(1) 93.61(17) 0086 The facile reaction of 31 with PCy Suggested that C(38)-Ru-N(3) 176.40(14) the pyridines may be displaced by other incoming ligands C(38)-Ru-N(4) 102.85 (14) C(38)-Ru-Cl(1) 93.83(12) and it was discovered that reaction of the bis-pyridine C(38)-Ru-Cl(2) 84.39(11) complex with a wide variety of phosphines provides a C(1)-Ru-N(3) 87.07(15) Simple and divergent route to new ruthenium benzylidenes C(1)-Ru-N(4) 161.18(14) C(1)-Ru-Cl(1) 100.57(14) of the general formula (ImesH)(PR)(Cl),Ru=CHPh. The C(1)-Ru-Cl(2) 84.75 (14) combination of 31 and 1.1 equiv. of PR results in a color Cl(1)-Ru-Cl(2) 174.50(4) change from green to redibrown and formation of the corresponding PR adduct. The residual pyridine can be removed under vacuum, and the ruthenium products are 0.083. Several structural isomers of the bis-pyridine purified by Several washes with pentane and/or by column adduct can be envisioned, but the Solid-state Structure chromotography. This ligand Substitution works well for a reveals that the pyridines bind in a cis geometry, occupying variety of alkyl- and aryl-Substituted phosphines including the coordination Sites trans to the benzylidene and the PPH, PBn, and P(n-Bu) to produce complexes 32, 33 and N-heterocyclic carbene ligand. The Ru-C(1) (benzylidene 34. US 2003/0069374A1 Apr. 10, 2003 20

equiv. of pyridine. The relatively large size of the iodide ligands and the lower electrophilicity at the metal center in 38 (as compared to 31) are both believed to contribute to the formation of a five-coordinate complex in this System. 0094 Complex 31 also reacts quantitatively with KTp Tp=tris(pyrazolyl)borate within 1 h at 25 C. to produce the bright green product Tp(ImesH)(Cl)Ru=CHPh (39), while the analogous reaction between complex 1 and KTp is Ru- Ph. extremely slow. (The latter proceeds to less than 50% Y completion even after several days at room temperature). Removal of the solvents under vacuum followed by filtration and several washes with pentane and provides 39 as an air and moisture stable solid. Preliminary "H NMR 0087 Z=Ph (32) Z=(p-CFCH) (35) studies also show that the combination of 31 with an excess of KO'-Bu produces the four-coordinate benzylidene, 0088 Z=Bn (33) Z=(p-CICH) (36) (ImesH)-(O'Bu)Ru=CHPh (40), quantitatively within 0089 Z=(n-Bu) (34) Z=(p-MeOCH) (37) 10 min. at ambient temperature. In contrast, the reaction 0090. Additionally, the para-substituted triphenylphos between 1 and KO'-Bu to form 40 does not proceed to phine derivatives 35, 36 and 37 (containing para Substituents completion, even after several days at 35 C. Complex 40 CF, Cl, and OMe, respectively) can be prepared using the may be considered a model for the 14-electron intermediate, inventive method. The synthetic accessibility of complex 35 (IMesH)(Cl),Ru=CHPh, involved in olefin metathesis is particularly remarkable, because P(p-CFCH) is an reactions of 1. extremely electron-poor phosphine (x=20.5 cm). The tri 0095 The invention provides a high-yielding procedure arylphosphine ruthenium complexes 32, 35-37 are valuable for the preparation of (IMesH)(Cl) (CHN)Ru=CHPh catalysts as they are almost 2 orders of magnitude more (31) from (IMesh)(CI) (PCy)Ru=CHPh (1). In contrast active for olefin metathesis reactions than the parent com to the reaction of 1 with olefinic Substrates, this ligand plex 1. Substitution proceeds by an associative mechanism. Com 0.091 There appear to be both steric and electronic limi pleX 31 reacts readily with phosphines, providing access to tations on the incoming phosphine ligand in the pyridine new complexes discussed herein. Complex 31 also under Substitution reaction. For example, complex 31 does not goes reaction with KO'-Bu, NaI, and KTp to provide new react with P(o-tolyl) to produce a stable product, presum four-, five-, and six-coordinate ruthenium benzylidenes. The ably due to the prohibitive size of the incoming ligand. The inventive methodology is useful for facilitating the devel cone angle of P(o-tolyl) is 194, while that of PCy (one of opment of new ruthenium olefin metathesis catalysts con the larger phosphines shown to Successfully displace the taining Structurally diverse ligand arrayS. pyridines of 31) is 170. Additionally, the electron-poor 0096 Olefin Metathesis: phosphine P(CF) shows no reaction with 31, even under 0097. The inventive complexes are useful in olefin met forcing conditions. This ligand has a significantly lower athesis reactions, particularly for polymerization reactions. electron donor capacity (=33.6 cm) than P(p-CFCH.) These catalysts can be used in various metathesis reactions, (X=20.5 cm) and also has a larger cone angle than PCys including but not limited to, ring-opening metathesis poly (0=184). merization of Strained and unstrained cyclic olefins, ring 0092. The methodology described herein represents a closing metathesis of acyclic dienes, acyclic diene metathe dramatic improvement over previous Synthetic routes to the sis polymerization ("ADMET), self- and cross-metathesis complexes (NHC)(PR)(Cl),Ru=CHPh. Earlier prepara reactions, polymerization, carbonyl olefination, tions of these compounds involved reaction of the bis depolymerization of unsaturated polymers, Synthesis of phosphine precursor (PR)(Cl),Ru=CHPh with an NHC telechelic polymers, and olefin Synthesis. ligand. These transformations were often low yielding (par 0098. The most preferred olefin monomer for use in the ticularly when the NHC was small), and required the parallel invention is Substituted or unsubstituted dicyclopentadiene Synthesis of ruthenium precursors containing each PR (DCPD). Various DCPD suppliers and purities may be used ligand. Furthermore, bis-phosphine Starting materials con such as Lyondell 108 (94.6% purity), Veliscol UHP (99.4% taining PR ligands that are Smaller and less electron purity), B. F. Goodrich Ultrene(R) (97% and 99% purities), donating than PPhi (0=145; X=13.25 cm; pK=2.73) can and Hitachi (99.4% purity). Other preferred olefin monomers not be prepared, placing Severe limitations on the complexes include other cyclopentadiene oligomers including trimers, that are available by the earlier preparation methods. tetramers, pentamers, and the like, cyclooctadiene (COD; 0093. The chlorine ligands of 31 are also substantially DuPont); cyclooctene (COE, Alfa Aesar); cyclohexenylnor labile relative to those in the parent complex 1. For example, bornene (Shell); norbornene (Aldrich); norbornene dicar 31 reacts quantitatively with NaI within 2 hours at room boxylic anhydride (nadic anhydride); norbornadiene (Elf temperature to afford (ImesH)(I) (CHN)Ru=CHPh Atochem); and Substituted norbornenes including butyl nor (38). In contrast, the reaction between 1 and NaI takes bornene, hexyl norbornene, octyl norbornene, decyl nor approximately 8 hours to reach completion under identical bornene, and the like. Preferably, the olefinic moieties conditions. Interestingly, H NMR spectroscopy reveals that include mono-or disubstituted olefins and cycloolefins con the diiodide complex 38 contains only one pyridine ligand, taining between 3 and 200 carbons. Most preferably, met while the analogous dichloride Species 31 coordinates 2 athesis-active olefinic moieties include Substituted or unsub US 2003/0069374A1 Apr. 10, 2003

Stituted cyclic or multicyclic olefins, for example, methano-1H-indene (i.e., reaction product of CPD and cyclopropenes, cyclobutenes, cycloheptenes, cyclooctenes, cyclopentene), 1,4,4,5,6,7,8,8-octahydro-1,4-methanonaph 2.2.1 bicycloheptenes, 2.2.2 bicyclooctenes, benzocy thalene (i.e., reaction product of CPD and cyclohexene), clobutenes, cyclopentenes, cyclopentadiene oligomers 14,4,5,6,7,8,9,10,10-decahydro-1,4-methanobenzocy including trimers, tetramers, pentamers, and the like, cyclo clooctene (i.e., reaction product of CPD and cyclooctene), hexenes. It is also understood that Such compositions and 1,2,3,3,3,4,7,7,8,8,decahydro-4,7-methanocyclopental include frameworks in which one or more of the carbon indene. atoms carry Substituents derived from radical fragments including halogens, pseudohalogens, alkyl, aryl, acyl, car 0100. These olefin monomers may be used alone or boxyl, alkoxy, alkyl- and arylthiolate, amino, aminoalkyl, mixed with each other in various combinations to adjust the and the like, or in which one or more carbon atoms have properties of the olefin monomer composition. For example, been replaced by, for example, Silicon, oxygen, Suilfr, nitro mixtures of cyclopentadiene dimer and trimerS offer a gen, phosphorus, antimony, or boron. For example, the reduced melting point and yield cured olefin copolymers olefin may be Substituted with one or more groups Such as with increased mechanical Strength and StiffneSS relative to thiol, thioether, ketone, aldehyde, ester, ether, amine, amide, pure poly-DCPD. AS another example, incorporation of nitro, carboxylic acid, disulfide, carbonate, isocyanate, phos COD, norbornene, or alkyl norbornene co-monomers tend to phate, phosphite, Sulfate, Sulfite, Sulfonyl, carbodiimide, yield cured olefin copolymers that are relatively Soft and carboalkoxy, carbamate, halogen, or pseudohalogen. Simi rubbery. The resulting polyolefin compositions formed from larly, the olefin may be Substituted with one or more groups the metathesis reactions are amenable to thermosetting and Such as C-Co alkyl, aryl, acyl, C-Co alkoxide, aryloxide, are tolerant of additives, Stabilizers, rate modifiers, hardneSS Cs-Co alkyldiketonate, aryldiketonate, C-C carboxylate, and/or toughness modifiers, fillers and fibers including, but arylsulfonate, C-C alkylsulfonate, C-Co alkylthio, not limited to, carbon, glass, aramid (e.g., Kevlar®) and Twaron(E), polyethylene (e.g., Spectrao and Dyneemae(E), arylthio, C-C alkylsulfonyl, and C-C alkylsulfinyl, polyparaphenylene benzobisoxazole (e.g., Zylon(R), poly C-Cao alkylphosphate, arylphosphate, wherein the moiety benzamidazole (PBI), and hybrids thereof as well as other may be substituted or unsubstituted. polymer fibers. 0099 Examples of preferred polymerizable norbornene type monomers include but are not limited to, norbornene 0101 The metathesis reactions may optionally include (bicyclo[2.2.1]hept-2-ene), 5-methyl-2-norbornene, ethyl formulation auxiliaries. Known auxiliaries include antistat norbornene, propylnorbornene, isopropylnorbornene, butyl ics, antioxidants (primary antioxidants, Secondary antioxi norbornene, isobutylnorbornene, pentylnorbornene, hexyl dants, or mixtures thereof), ceramics, light stabilizers, plas norbornene, heptylnorbornene, octylnorbornene, ticizers, dyes, pigments, fillers, reinforcing fibers, lubricants, decylnorbornene, dodecylnorbornene, octadecylnorbornene, adhesion promoters, Viscosity-increasing agents, and p-tolylnorbornene, methylidene norbornene, phenylnor demolding enhancers. Illustrative examples of fillers for bornene, ethylidenenorbornene, Vinylnorbornene, exo-dicy improving the optical physical, mechanical, and electrical clopentadiene, endo-dicyclopentadiene, tetracyclododecene, properties include glass and quartz in the form of powders, methyltetracyclododecene, tetracyclododecadiene, dimeth beads, and fibers, metal and Semi-metal oxides, carbonates yltetracyclododecene, ethyltetracyclododecene, ethylidenyl (e.g. MgCO, CaCO), dolomite, metal Sulfates (e.g. gyp tetracyclododecene, phenyltetracyclodecene, Symmetrical Sum and barite), natural and Synthetic Silicates (e.g. Zeolites, and unsymmetrical trimers and tetramers of cyclopentadi wollastonite, and feldspars), carbon fibers, and plastics ene, 5,6-dimethylnorbornene, propenylnorbornene, 5,8-me fibers or powders. thylene-5a,8a-dihydrofluorene, cyclohexenylnorbornene, 0102) The UV and oxidative resistance of the polyolefin dimethanohexahydronaphthalene, endo,eXO-5,6-dimethoX compositions resulting from the metathesis reactions using ynorbornene, endo,endo-5,6-dimethoxynorbornene, 2,3- the inventive carbene complex may be enhanced by the dimethoxynorbornadiene, 5,6-bis(chloromethyl)bicyclo addition of various Stabilizing additives Such as primary 2.2.1]hept-2-ene, 5-tris(ethoxy)silylnorbornene, antioxidants (e.g., Sterically hindered phenols and the like), 2-dimethylsilylbicyclo2.2.1]hepta-2,5-diene, 2,3-bistrifluo Secondary antioxidants (e.g., organophosphites, , romethylbicyclo2.2.1]hepta-2,5-diene, 5-fluoro-5-pen and the like), light Stabilizers (e.g., hindered amine light tafluoroethyl-6-6-bis(trifluoromethyl)bicyclo[2.2.1]hept-2- stabilizers or HALS), and UV light absorbers (e.g., hydroxy ene, 5,6-difluoro-5-heptatafluoroisopropyl-6- benzophenone absorbers, hydroxyphenylbenzotriazole trifluoromethyl)bicyclo2.2. Ilhept-2-ene, 2,3,3,4,4,5,5,6- octafluorotricyclo5.2.1.0dec-8-ene, and absorbers, and the like), as described in U.S. application Ser. 5-trifluoromethylbicyclo2.2.1]hept-2-ene, 5,6-dimethyl-2- No. 09/498,120, filed Feb. 4, 2000, the contents of which are norbornene, 5-a-naphthyl-2-norbornene, 5,5-dimethyl-2- incorporated herein by reference. norbornene, 1,44a,9.9a, 10-hexahydro-9,101,2-benzeno 0.103 Exemplary primary antioxidants include, for 1,4-methanoanthracene. indanylnorbornene (i.e., 1,44.9- example, 4,4'-methylenebis (2,6-di-tertiary-butylphenol) tetrahydro-1,4-methanofluorene, the reaction product of (Ethanox 702(R); Albemarle Corporation), 1,3,5-trimethyl-2, CPD and indene), 6,7,10,10-tetrahydro-7,10-methanofluo 4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (Etha ranthene (i.e., the reaction product of CPD with acenaph nox 330(R); Albermarle Corporation), octadecyl-3-(3',5'-di thalene), 1.4.4.9,9,10-hexahydro-9,101,2-benzeno-1,4- tert-butyl-4'-hydroxyphenyl) propionate (Irganox 1076(R); methanoanthracene, endo.endo-5,6-dimethyl-2-norbornene, Ciba-Geigy), and pentaerythritol tetrakis(3-(3,5-di-tert-bu endo.eXO-5,6-dimethyl-2-norbornene, eXO.eXO-5,6-dim tyl-4-hydroxyphenyl)propionate)(Irganox(R) 1010; Ciba ethyl-2-norbornene, 1,4,4,5,6,9,10,13,14, 14-decahydro-1,4- Geigy). Exemplary Secondary antioxidants include tris(2,4- methanobenzocyclododecene (i.e., reaction product of CPD ditert-butylphenyl)phosphite (Irgafos(R 168; Ciba-Geigy), and 1.5.9-cyclododecatriene), 2,3,3,4,7,7-hexahydro-4,7- 1:11(3,6,9-trioxaudecyl)bis(dodecylthio)propionate (Wing US 2003/0069374A1 Apr. 10, 2003 22 stay(R) SN-1; Goodyear), and the like. Exemplary light 0108. The inventive metal carbene complexes have Stabilizers and absorbers include bis(1,2,2,6,6-pentamethyl shown a high rate of initiation allowing for most, if not all, 4-piperidinyl)-3,5-bis(1,1-dimethylethyl)-4-hydroxyphe of the complex added to the reaction to be consumed. Thus, nyl)methylbutylmalonate (Tinuvin(R) 144 HALS; Ciba leSS catalyst is wasted in the metathesis reaction. In contrast, Geigy), 2-(2H-benzotriazol-2-yl)-4,6-ditertpentylphenol the previous pentacoordinated initiators had a higher amount (Tinuvin(R) 328 absorber; Ciba-Geigy), 2,4-di-tert-butyl-6- of extractibles (i.e. unpolymerized monomer) remaining (5-chlorobenzotriazol-2-yl)phenyl (Tinuvin(R) 327 absorber; after the reaction concluded. The rate of propogation is also Ciba-Geigy), 2-hydroxy-4-(octyloxy)benzophenone (Chi slowed by the presence of the two pyridine ligands. The high massorb(R 81 absorber; Ciba-Geigy), and the like. rate of initiation and low rate of propagation yields polymers 0104. In addition, a suitable rate modifier such as, for with narrow polydisperities relative to those achieved with example, triphenylphosphine (TPP), tricyclopentylphos the earlier pentacoordinated complexes. Moreover, it was phine, tricyclohexylphosphine, triisopropylphosphine, tri determined that heat increases the rate of the initiation. alkylphosphites, triarylphosphites, mixed phosphites, or Thermal initiation of the pentacoordinated complexes can be other Lewis base, as described in U.S. Pat. No. 5,939.504 seen in U.S. Pat. No. 6,107,420, the contents of which are and U.S. application Ser. No. 09/130,586, the contents of incorporated herein by reference. In general, the initiation each of which are herein incorporated by reference, may be and/or rate of the metathesis polymerization using the inven added to the olefin monomer to retard or accelerate the rate tive catalysts is controlled by a method comprising contact of polymerization as required. ing the inventive catalyst with an olefin and heating the 0105 The resulting polyolefin compositions, and parts or reaction mixture. In a Surprising and unexpected result, the articles of manufacture prepared therefrom, may be pro T for the thermal initiation of the inventive catalyst is cessed in a variety of ways including, for example, Reaction Significantly higher than the T for the previous pentaco Injection Molding (RIM), Resin Transfer Molding (RTM) ordinated catalysts. Without being bound by theory, this is and vacuum-assisted variants such as VARTM (Vacuum Significant in that in a reaction using a metathesis catalyst, Assisted RTM) and SCRIMP (Seemann Composite Resin if the part or article being prepared is a type of filled System Infusion Molding Process), open casting, rotational mold (e.g., a System containing reinforcing fillers, fibers, beads, ing, centrifugal casting, filament winding, and mechanical etc.), the filling material may act as a heat sink. With the machining. These processing compositions are well known previous pentacoordinated catalysts, post-curing was Some in the art. Various molding and processing techniques are times necessary due to the effect of the heat Sink resulting described, for example, in PCT Publication WO97/20865, from a filled system. ROMP polymerization in the presence and U.S. Provisional Patent Application No. 60/360,755, of peroxide cross linking agents using pentacoordinated filed Mar. 1, 2002 and entitled “Polymer Processing Meth catalysts is discussed in U.S. Pat. No. 5,728,785, the con ods and Techniques Using Pentacoordinated or Hexacoor tents of which are incorporated herein by reference. In contrast, the reactions using the inventive hexacoordinated dinated Ruthenium or Osmium Metathesis Catalysts,” the catalysts generate significantly more internal heat. This high disclosures of which is incorporated herein by reference. T. reduces the need for post cure. Additionally, even if 0106 The metathesis reactions may occur in the presence peroxides or radicals are added to promote crosslinking, the or absence of a Solvent. Examples of Solvents that can be degree of crosslinking in the part that uses the radical used in the polymerization reaction include organic, protic, mechanism is increased in comparison to a part prepared or aqueous Solvents, which are preferably inert under the using the previous pentacoordinated metathesis catalysts. polymerization conditions. Examples of Such Solvents Moreover, the half-life is dependent on the maximum tem include aromatic hydrocarbons, chlorinated hydrocarbons, perature. Using the inventive catalysts, the half life is , aliphatic hydrocarbons, , water, or mixtures reduced Substantially, and therefore leSS catalyst is needed, thereof. Preferred Solvents include benzene, toluene, p-Xy providing a significant commercial advantage. Without lene, methylene chloride, dichloroethane, dichlorobenzene, being bound by theory, the higher T indicates that in a chlorobenzene, tetrahydrofuran, diethylether, pentane, ROMP reaction, more rings are opened, and there is a better methanol, ethanol, water or mixtures thereof. More prefer degree of cure. With a higher T, the extractibles are ably, the Solvent is benzene, toluene, p-Xylene, methylene almost to Zero, indicating that almost every molecule that chloride, dichloroethane, dichlorobenzene, chlorobenzene, can be reacted is reacted. For example, the vinylidenes are tetrahydrofuran, diethylether, pentane, methanol, ethanol, or advantageous in that they are more Stable at higher tem mixtures thereof. Most preferably, the solvent is toluene, or peratures than the alkylidenes. When the protected NHC a mixture of benzene and methylene chloride. The solubility (e.g., a Saturated Imes ligand as described in U.S. Provi of the polymer formed in the polymerization reaction will sional Patent Application Nos. 60/288,680 and 60/278,311, depend on the choice of Solvent and the molecular weight of the contents of each of which are incorporated herein by the polymer obtained. reference), is added to the reaction mixture, a dramatic increase in peak exotherm is seen. Additionally, the time to 0107 The inventive complexes have a well-defined reach the peak is significantly reduced. A high peak eXo ligand environment that enables flexibility in modifying and therm means more catalyst is available for polymerization, fine-tuning the activity level, Stability, Solubility and ease of indicating that the extractibles are close to Zero. Accord recovery of these catalysts. The solubility of the carbene ingly, the inventive catalysts have better conversion, better compounds may be controlled by proper Selection of either properties, even in the presence of fillers and additives. hydrophobic or hydrophilic ligands as is well known in the art. The desired solubility of the catalyst will largely be 0109 For the purposes of clarity, the specific details of determined by the solubility of the reaction substrates and the invention will be illustrated with reference to especially reaction products. preferred embodiments. However, it should be appreciated US 2003/0069374A1 Apr. 10, 2003

that these embodiments and examples are for the purposes of pentane, and dried under Vacuum to afford illustration only and are not intended to limit the Scope of the (IMesH)(CHN)(Cl),Ru=CHPh 7 as a light green invention. powder (1.9 gram, 93% yield). 0120 "H NMR (300 MHz, CDC1): 8 19.05 (s, 1H, EXAMPLES CHPh), 8.31 (d. 2H, pyridine CH, J-6.6 Hz), 7.63 (d. 2H, 0110 General Procedures ortho CH, J=8.4 Hz), 7.49 (t, 1H, para CH, J=7.4 Hz), 7.33 (d. 2H, pyridine CH, J–6.9 Hz), 7.10 (t, 2H, meta 0111. Manipulation of organometallic compounds was CH, J-8.0 Hz), 7.03 (br. S, 2H, Mes CH), 6.78 (br. S, 2H, performed using Standard Schlenk techniques under an Mes CH), 6.36 (d. 2H, pyridine CH, J–6.3 Hz), 6.05 (d. atmosphere of dry argon or in a nitrogen-filled Vacuum 2H, pyridine CH, J–6.9 Hz), 4.08 (br. d, 4H, Atmospheres drybox (O<2 ppm). NMR spectra were NCHCHN), 3.30 (m, 4H, pyrrolidine CH), 3.19 (m, 4H, recorded on a Varian Inova (499.85 MHz for H; 202.34 pyrrolidine CH-), 2.61-2.22 (multiple peaks, 18H, Mes MHz for P; 125.69 MHz for 'C) or a Varian Mercury 300 CH), 2.02 (m, 4H, pyrrolidine CH), 1.94 (m, 4H, pyrro (299.817 for H; 121.39 MHz for P; 74.45 MHz for 'C). 'P NMR spectra were referenced using HPO, (Ö=0 ppm) lidine CH-). as an external Standard. UV-vis Spectra were recorded on an 0121 Example: A 75 gram mass of DCPD (containing HP 8452A diode-array spectrophotometer. about 24% trimerized DCPD) was polymerized using (IMesH)(CHN)(Cl),Ru=CHPh=0.0151 grams at a 0112 Materials and Methods DCPD:Ruratio of (about 30,000:1) at a starting temperature 0113 Pentane, toluene, benzene, and benzene-d were of about 24.2 C. Result: Time to reach maximum tempera dried by passage through Solvent purification columns. ture (T)=194 seconds. T=208.9 C. Glass transition Pyridine was dried by vacuum transfer from CaH. All temperature measured by "thermal mechanical analysis phosphines as well as KTp were obtained from commercial (TMA)=165 C. Percent residual monomer (toluene extrac Sources and used as received. Ruthenium complexes 1-4 and tion at room temperature)=1.23%. 44-48 were prepared according to literature procedures. 0122) Synthesis of (IMesH)(CHN)(Cl),Ru=CHPh 0114 Synthesis of (IMesh)(CIHN)(Cl),Ru=CHPh 0123 Complex 1 (2.0 grams) was dissolved in toluene 0115 Complex 1 (2.0 grams) was dissolved in toluene (10 mL), and 4-methylpyridine (0.88 grams, 4 mol equiva (10 mL), and 1,10-phenanthroline (0.85 grams, 2 mol lents) was added. The reaction flask was purged with argon equivalents) was added. The reaction flask was purged with and the reaction mixture was stirred for approximately 12 argon and the reaction mixture was stirred for approximately hours at about 20° C. to about 25 C. during which time a 12 hours at about 20° C. to about 25 C. during which time color change from dark purple to light green was observed. a color change from dark purple to brown-orange was The reaction mixture was transferred into 75 mL of cold observed. The reaction mixture was transferred into 75 mL (about 0. C.) pentane, and a light green Solid precipitated. of cold (about 0. C.) pentane, and a brown-orange Solid The precipitate was filtered, washed with 4x20 mL of cold precipitated. The precipitate was filtered, washed with 4x20 pentane, and dried under Vacuum to afford mL of cold pentane, and dried under Vacuum to afford (IMesH)(CHN)(Cl),Ru=CHPh8 as an light green pow (IMesH)(CHN)(Cl),Ru=CHPh 5 as an brown-orange der (1.5 grams, 84% yield). powder (1.7 gram, 96% yield). 0124) Synthesis of (IMesh)(CHN)(Cl),Ru=CHPh 0116 Synthesis of (IMesh)(CHBrN)(Cl),Ru=CIPh 0125 Complex 1 (2.0 grams) was dissolved in toluene 0117 Complex 1 (2.0 grams) was dissolved in toluene (10 mL), and 4,4'-bipyridine (0.74 grams, 2 molecquivalents) (10 mL), and 3-bromopyridine (1.50 grams, 4 mol equiva was added. The reaction flask was purged with argon and the lents) was added. The reaction flask was purged with argon reaction mixture was Stirred for approximately 12 hours at and the reaction mixture was stirred for approximately 12 about 20° C. to about 25 C. during which time a color hours at about 20° C. to about 25 C. during which time a change from dark purple to brown-orange was observed. color change from dark purple to light green was observed. The reaction mixture was transferred into 75 mL of cold The reaction mixture was transferred into 75 mL of cold (about 0. C.) pentane, and an brown-orange Solid precipi (about 0. C.) pentane, and a light green Solid precipitated. tated. The precipitate was filtered, washed with 4x20 mL of The precipitate was filtered, washed with 4x20 mL of cold cold pentane, and dried under vacuum to afford pentane, and dried under Vacuum to afford (IMesH)(CHN)(Cl),Ru=CHPh9 as a brown-orange (IMesH)(CHBrN)(Cl),Ru=CHPh 6 as a light green powder (1.4 gram, 71% yield). powder (1.8 grams, 86% yield). 0126) "H NMR (500 MHz, CDC1): 8 19.15 (s, 1H, 0118 Synthesis of (IMesh)(CHN)(Cl),Ru=CHPh CHPh), 8.73-8.68 (multiple peaks, 8H, pyridine CH), 7.63 0119) Complex 1 (2.0 grams) was dissolved in toluene 6.77 (multiple peaks, 17H, pyridine CH, para CH, meta CH, (10 mL), and 4-pyrrolidinopyridine (1.40 grams, 4 mol Mes CH), 4.08 (br. d, 4H, NCHCHN), 2.61-2.24 (multiple equivalents) was added. The reaction flask was purged with peaks, 18H, Mes CH). argon and the reaction mixture was stirred for approximately 0127 Polymerization Example: A 75 gram mass of 12 hours at about 20° C. to about 25 C. during which time DCPD (containing about 24% trimerized DCPD) was poly a color change from dark purple to light green was observed. merized using (IMesh)(CHN)(Cl),Ru=CHPh= The reaction mixture was transferred into 75 mL of cold 0.0153 grams at a DCPD:Ruratio of (about 30,000:1) at a (about 0. C.) pentane, and a light green Solid precipitated. starting temperature of about 24.2 C. Result: Time to reach The precipitate was filtered, washed with 4x20 mL of cold maximum temperature (T)=953 seconds. T=124.2 C. US 2003/0069374A1 Apr. 10, 2003 24

0128 Synthesis of (IMesh)(CHN)(Cl),Ru=CHPh color change from dark purple to dark green was observed. 0129 Complex 1 (2.0 grams) was dissolved in toluene The reaction mixture was transferred into 75 mL of cold (10 mL), and 4-dimethylaminopyridine (1.18 grams, 4 mol (about 0. C.) pentane, and a dark green Solid precipitated. equivalents) was added. The reaction flask was purged with The precipitate was filtered, washed with 4x20 mL of cold argon and the reaction mixture was Stiffed for approximately pentane, and dried under Vacuum to afford 12 hours at about 20° C. to about 25 C. during which time (IMesH)(CHN)(Cl),Ru=CHPh 13 as a dark green a color change from dark purple to light green was observed. powder (2.0 grams, 97% yield). The reaction mixture was transferred into 75 mL of cold 0138 H NMR (500 MHz, CDC1): 8 19.23 (s, 1H, (about 0. C.) pentane, and a light green Solid precipitated. CHPh), 8.74 (br. S, 2H, pyridine), 7.91 (br. S, 2H, pyridine), The precipitate was filtered, washed with 4x20 mL of cold 7.70-7.08 (multiple peaks, 19H, ortho CH, para CH, meta pentane, and dried under Vacuum to afford CH, pyridine), 6.93 (br. S, 2H, Mes CH) 6.79 (br.s, 2H, Mes (IMesH)(CHN)(Cl),Ru=CHPh 10 as a light green CH), 4.05 (br. s, 4H, NCHCHN), 2.62-2.29 (multiple powder (1.9 gram, 99% yield). peaks, 18H, Mes CH). 0130 H NMR (500 MHz, CDC1): 8 19, 10 (s, 1H, 0.139 Polymerization Example: A 75 gram mass of CHPh), 8.18 (d, 2H, pyridine CH, J–6.5 Hz), 7.64 (d. 2H, DCPD (containing about 24% trimerized DCPD) was poly ortho CH, J-7.5 Hz), 7.48 (t, 1H, para CH, J-7.0 Hz), merized using (IMesH)(CHN)(Cl),Ru=CHPh=0.0153 7.38 (d. 2H, pyridine CH, J–6.5 Hz), 7.08 (t, 2H, meta grams at a DCPD:Ruratio of (about 30,000:1) at a starting CH, J-7.5 Hz), 7.00 (br.s, 2H, Mes CH), 6.77 (br.s, 2H, temperature of about 13.4 C. Mes CH), 6.49 (d. 2H, pyridine CH, J-6.0 Hz), 6.15 (d. 2H, pyridine CH, J-7.0 Hz), 4.07 (br. d, 4H, 0140 Result: Time to reach maximum temperature NCHCHN), 2.98 (s, 6H, pyridine CH-), 2.88 (s, 6H, (T)=145 seconds. T=202.2 C. Glass transition tem pyridine CH-), 2.61-2.21 (multiple peaks, 18H, Mes CH). perature measured by thermal mechanical analysis (TMA)= 0131 Polymerization Example: A 75 gram mass of 168° C. Percent residual monomer (toluene extraction at DCPD (containing about 24% trimerized DCPD) was poly room temperature)=1.17%. merized using (IMesh)(CHN)(Cl),Ru=CHPh= 0141 Synthesis of 0.0141 grams at a DCPD:Ruratio of (about 30,000:1) at a (IMesH)(CHN)(Cl),Ru=CHPh starting temperature of about 24.2 C. Result: Time to reach maximum temperature (T)=389 seconds. T=175.3 C. 0142 Complex 1 (2.0 grams) was dissolved in toluene (10 mL), and 2,2'-biquinoline (1.21 grams, 2 mol equiva 0132) Synthesis of (IMesH)(CHN)(Cl),Ru=CHPh lents) was added. The reaction flask was purged with argon 0133) Complex 1 (2.0 grams) was dissolved in toluene and the reaction mixture was stirred for approximately 12 (10 mL), and 2,2'-bipyridine (0.74 grams, 2 molecquivalents) hours at about 20° C. to about 25 C. during which time a was added. The reaction flask was purged with argon and the Slight color change from dark purple to brown-purple was reaction mixture was Stirred for approximately 12 hours at observed. The reaction mixture was transferred into 75 mL about 20° C. to about 25 C. during which time a color of cold (about 0° C) pentane, and a brown-purple solid change from dark purple to brown-red was observed. The precipitated. The precipitate was filtered, washed with 4x20 reaction mixture was transferred into 75 mL of cold (about mL of cold pentane, and dried under Vacuum to afford 0° C.) pentane, and an brown-red solid precipitated. The (IMesH)(CHN)(Cl),Ru=CHPh 14 as a brown precipitate was filtered, washed with 4x20 mL of cold purple powder (1.8 gram, 93% yield). pentane, and dried under Vacuum to afford (IMesH)(CHN)(Cl),Ru=CHPh 11 as a brown-red 0143) Synthesis of (IMesH)(CHN)(Cl),Ru=CHPh powder (0.7 gram, 41% yield). 0144) Complex 1 (1.1 g, 1.3 mmol) was dissolved in toluene, and pyridine (10 mL) was added. The reaction was 0134) Synthesis of (IMesH)(CHNO)(Cl),Ru=CHPh Stirred for 10 min during which time a color change from 0135 Complex 1 (2.0 grams) was dissolved in toluene pink to bright green was observed. The reaction mixture was (10 mL), and 2-pyridinecarboxaldehyde (1.01 grams, 4 mol cannula transferred into 75 mL of cold (about 0°C.) pentane, equivalents) was added. The reaction flask was purged with and a green Solid precipitated. The precipitate was filtered, argon and the reaction mixture was stirred for approximately washed with 4x20 mL of pentane, and dried under vacuum 12 hours at about 20° C. to about 25 C. during which time to afford (IMesH)(CHN)(Cl),Ru=CHPh as a green a color change from dark purple to dark blue was observed. powder (0.75 g, 80% yield). Samples for elemental analysis The reaction mixture was transferred into 75 mL of cold were prepared by recrystallization from C. He/pentane fol (about 0°C.) pentane, and a dark blue solid precipitated. The lowed by drying under vacuum. These samples analyze as precipitate was filtered, washed with 4x20 mL of cold the monopyridine adduct pentane, and dried under Vacuum to afford (IMesH)(CHN)(Cl),Ru=CHPh, probably due to loss of (IMesH)(CHNO)(Cl),Ru=CHPh 12 as a dark blue pyridine under vacuum. "H NMR (CH): a 19.67 (s, 1H, powder (1.3 gram, 70% yield). CHPh), 8.84 (br. S, 2H, pyridine), 8.39 (br. S, 2H, pyridine), 8.07 (d. 2H, ortho CH, J–8 Hz), 7.15 (t, 11H, para CH, 0136) Synthesis of (IMesH)(CHN)(Cl),Ru=CHPh J=7 Hz), 6.83-6.04 (br multiple peaks, 9H, pyridine, and 0137) Complex 1 (2.0 grams) was dissolved in toluene Mes CH), 3.37 (br d, 4H, CHCH), 2.79 (brs, 6H, Mes (10 mL), and 4-phenylpyridine (1.50 grams, 4 mol equiva CH), 2.45 (brs, 6H, Mes CH), 2.04 (brs, 6H, Mes CH). lents) was added. The reaction flask was purged with argon 'C{H}NMR(CD): a 314.90 (m, Ru=CHPh), 219.10 (s, and the reaction mixture was stirred for approximately 12 Ru–C(N)), 152.94, 150.84, 139.92, 138.38, 136.87, hours at about 20° C. to about 25 C. during which time a 135.99, 134.97, 131.10, 130.11, 129.88, 128.69, 123.38, US 2003/0069374A1 Apr. 10, 2003

51.98, 51.37, 21.39, 20.96, 19.32. Anal. Calcd for 0154) Synthesis of (PCp)(CHN)(Cl),Ru=CH C.H.NCIRu: C, 61.20; H, 5.76; N, 6.49. Found: C, CH=C(CH.) 61.25; H, 5.76; N, 6.58. 0155 Complex 2 (2.0 grams) was dissolved in toluene 0145 Polymerization Example: A 75 gram mass of (10 mL), and 4-methylpyridine (1.04 grams, 4 mol equiva DCPD (containing about 24% trimerized DCPD) was poly lents) was added. The reaction flask was purged with argon merized using (IMesH)(CHN)(Cl),Ru=CHPh=0.0127 and the reaction mixture was stirred for approximately 12 grams at a DCPD:Ruratio of (about 30,000:1) at a starting hours at about 20° C. to about 25 C. during which time a temperature of about 12.1 C. Result: Time to reach maxi color change from dark purple to light green was observed. mum temperature (T)=173 seconds. T=201.9 C. The reaction mixture was transferred into 75 mL of cold Glass transition temperature measured by thermal mechani (about 0. C.) pentane, and a light green Solid precipitated. cal analysis (TMA)=164° C. Percent residual monomer The precipitate was filtered, washed with 4x20 mL of cold (toluene extraction at room temperature)=1.05%. pentane, and dried under Vacuum to afford 0146 Polymerization Example: A50 gram mass of hexy (PCp)(CHN)-(Cl),Ru=CH-CH=C(CH4), 18 as a light lnorbornene WS polymerized using green powder (1.4 gram, 75% yield). (IMesH)(CHN)(Cl),Ru=CHPh=0.0068 grams at a 0156 Synthesis of (PCy)(CHN)(Cl),Ru=CH HN:Ruratio of (about 30,000:1) at a starting temperature of CH=C(CH.) about 12.2 C. 0157 Complex 3 (2.0 grams) was dissolved in toluene 0147 Result: Time to reach maximum temperature (10 mL), and 1,10-phenanthroline (0.91 grams, 2 mol (T)=99 seconds. T=140.7° C. equivalents) was added. The reaction flask was purged with argon and the reaction mixture was stirred for approximately 0148 Synthesis of (PCp)(CHN)(Cl),Ru=CH 12 hours at about 20° C. to about 25 C. during which time CH=C(CH), a color change from dark purple to orange-brown was 0149 Complex 2 (2.0 grams) was dissolved in toluene observed. The reaction mixture was transferred into 75 mL (10 mL), and 1,10-phenanthroline (1.01 grams, 2 mol of cold (about 0° C.) pentane, and an orange-brown Solid equivalents) was added. The reaction flask was purged with precipitated. The precipitate was filtered, washed with 4x20 argon and the reaction mixture was stirred for approximately mL of cold pentane, and dried under Vacuum to afford 12 hours at about 20° C. to about 25 C. during which time (PCy)(C2HN)(Cl),Ru=CH-CH=C(CH4). 19 as an a color change from dark purple to red-brown was observed. orange-brown powder (1.7 gram, 97% yield). The reaction mixture was transferred into 75 mL of cold (about 0. C.) pentane, and a red-brown Solid precipitated. 0158 Synthesis of (PCy)(CHBrN)(Cl),Ru=CH The precipitate was filtered, washed with 4x20 mL of cold CH=C(CH), pentane, and dried under Vacuum to afford 0159 Complex 3 (2.0 grams) was dissolved in toluene (PCp)(CHN)(Cl),Ru=CH-CH=C(CH4), 15 as an (10 mL), and 3-bromopyridine (1.58 grams, 4 mol equiva red-brown powder (1.8 gram, 98% yield). lents) was added. The reaction flask was purged with argon and the reaction mixture was stirred for approximately 12 0150. Synthesis of (PCp)(CHBrN)(Cl),Ru=CH hours at about 20° C. to about 25 C. during which time no CH=C(CH.) dramatic color change from dark purple was observed. The 0151 Complex 2 (2.0 grams) was dissolved in toluene reaction mixture was transferred into 75 mL of cold (about (10 mL), and 3-bromopyridine (1.76 grams, 4 mol equiva 0 C.) pentane, and a purple Solid precipitated. The precipi lents) was added. The reaction flask was purged with argon tate was filtered, washed with 4x20 mL of cold pentane, and and the reaction mixture was stirred for approximately 12 dried under WCUU to afford hours at about 20° C. to about 25 C. during which time a (PCy)(C.H. BrN)-(Cl),Ru=CH-CH=C(CH4). 20 as a color change from dark purple to green was observed. The purple powder (1.4 gram, 67% yield). reaction mixture was transferred into 75 mL of cold (about 0 C.) pentane, and a green Solid precipitated. The precipi 0.160) Synthesis of (PCy)(CHN)(Cl),Ru=CH tate was filtered, washed with 4x20 mL of cold pentane, and CH=C(CH.) dried under WCUU to afford 0161 Complex 3 (2.0 grams) was dissolved in toluene (PCp)(C.H. BrN).(Cl),Ru=CH-CH=C(CH4), 16 as an (10 mL), and 4-phenylpyridine (1.55 grams, 4 mol equiva green powder (0.2 gram, 10% yield). lents) was added. The reaction flask was purged with argon and the reaction mixture was stirred for approximately 12 0152 Synthesis of (Cp)(CHN)(Cl),Ru=CH hours at about 20° C. to about 25 C. during which time a CH=C(CH.) color change from dark purple to brown was observed. The 0153 Complex 2 (2.0 grams) was dissolved in toluene reaction mixture was transferred into 75 mL of cold (about (10 mL), and pyridine (0.88 grams, 4 mol equivalents) was 0 C.) pentane, and a brown Solid precipitated. The precipi added. The reaction flask was purged with argon and the tate was filtered, washed with 4x20 mL of cold pentane, and reaction mixture was Stirred for approximately 12 hours at dried under WCUU to afford about 20° C. to about 25 C. during which time a color (PCy)(C, H.N).(Cl),Ru=CH-CH=C(CH4), 21 as a change from dark purple to green was observed. The reac brown powder (1.6 gram, 77% yield). tion mixture was transferred into 75 mL of cold (about 0°C.) pentane, and a green Solid precipitated. The precipitate was 0162 Synthesis of (PCy)(CHN)(Cl),Ru=CH filtered, washed with 4x20 mL of cold pentane, and dried CH=C(CH.) under vacuum to afford (PCp)(CHN)(Cl),Ru=CH 0163 Complex 3 (2.0 grams) was dissolved in toluene CH=C(CH3)2 17 as a green powder (0.6 gram, 34% yield). (10 mL), and 4-methylpyridine (0.93 grams, 4 mol equiva US 2003/0069374A1 Apr. 10, 2003 26 lents) was added. The reaction flask was purged with argon reaction mixture was transferred into 75 mL of cold (about and the reaction mixture was stirred for approximately 12 0 C.) pentane, and a green Solid precipitated. The precipi hours at about 20° C. to about 25 C. during which time a tate was filtered, washed with 4x20 mL of cold pentane, and color change from dark purple to green was observed. The dried under WCUU to afford reaction mixture was transferred into 75 mL of cold (about (IMesH)(C.H.N.).(Cl),Ru=CH-CH=C(CH4), 25 as a 0 C.) pentane, and a green Solid precipitated. The precipi green powder (1.0 gram, 65% yield). tate was filtered, washed with 4x20 mL of cold pentane, and dried under WCUU to afford 0172) H NMR (300 MHz, CDC1): 8 19.05 (d.1H, (PCy)(C.H.N).(Cl),Ru=CH-CH=C(CH4), 22 as a CH-CH=C(CH), J-11 Hz), 8.14 (br. S, 2H, pyridine green powder (1.6 gram, 91% yield). CH), 7.69 (d. 1H, CH-CH=C(CH), J=11 Hz), 7.36 (d, 2H, pyridine CH, J-6.0 Hz), 7.04 (s, 2H, Mes CH), 0164. Synthesis of (PCy)(CHN)(Cl),Ru=CH 6.81 (s, 2H, Mes CH), 6.36 (br.s, 2H, pyridine CH), 6.12 (d, CH=C(CH.) 2H, pyridine CH, J-6.0 Hz), 4.06 (m. d, 4H, 0165 Complex 3 (2.0 grams) was dissolved in toluene NCHCHN), 3.29 (br. s, 4H, pyrrolidine CH), 3.23 (br. s. (10 mL), and pyridine (0.79 grams, 4 mol equivalents) was 4H, pyrrolidine CH-), 2.55-2.12 (multiple peaks, 18H, Mes added. The reaction flask was purged with argon and the CH), 2.02 (br. S., 4H, pyrrolidine CH-), 1.97 (br. S, 4H, reaction mixture was Stirred for approximately 12 hours at pyrrolidine CH-), 1.10(S,3H, CH-CH=C(CH)), 1.08 (s, about 20° C. to about 25 C. during which time a color 3H, CH-CH=C(CH)). change from dark purple to light green was observed. The 0173 Polymerization Example: A 75 gram mass of reaction mixture was transferred into 75 mL of cold (about DCPD (containing about 24% trimerized DCPD) was poly 0 C.) pentane, and a light green Solid precipitated. The merized using (Mesh)(CHN)(Cl),Ru=CH precipitate was filtered, washed with 4x20 mL of cold CH=C(CH)=0.0147 grams at a DCPD:Ruratio of (about pentane, and dried under Vacuum to afford 30,000:1) at a starting temperature of about 24.7 C. (PCy)(C.H.N).(Cl),Ru=CH-CH=C(CH4), 23 as a light green powder (1.4 gram, 83% yield). 0.174 Result: Time to reach maximum temperature (T)=181 seconds. T=200.9 C. Glass transition tem 0166 Polymerization Example: A 75 gram mass of perature measured by thermal mechanical analysis (TMA)= DCPD (containing about 24% trimerized DCPD) was poly 144° C. Percent residual monomer (toluene extraction at merized using (PCy)(CHN)(Cl),Ru=CH room temperature)=3.93%. CH=C(CH)=0.0237 grams at a DCPD:Ruratio of (about 0175 Synthesis of (IMesH)(CHN)(Cl),Ru=CH 15,000:1) at a starting temperature of about 52.2° C. CH=C(CH.) 0167 Result: Time to reach maximum temperature 0176 Complex 4 (1.5 grams) was dissolved in toluene (T)=1166 seconds. T=60.2 C. (10 mL), and 4,4'-bipyridine (0.57 grams, 2 mot equivalents) 0168 Polymerization Example: A 75 gram mass of was added. The reaction flask was purged with argon and the DCPD (containing about 24% trimerized DCPD) was poly reaction mixture was stirred for approximately 2 hours at merized using (PCy)(CHN)(Cl),Ru=CH about 20° C. to about 25 C. during which time no dramatic CH=C(CH)=0.0237 grams in the presence of sImesH color change from brown was observed. The reaction mix CCl=0.0297 grams at a DCPD:RuislimesHCCls ratio of ture was transferred into 75 mL of cold (about 0° C.) (about 15,000:1:2) at a starting temperature of about 49.4 pentane, and a brown Solid precipitated. The precipitate was C. Result: Time to reach maximum temperature (T)=715 filtered, washed with 4x20 mL of cold pentane, and dried seconds. T=173.3 C. under WCUU tO afford (IMesH)(CHN).(Cl),Ru=CH-CH=C(CH4), 26 as a 0169. Synthesis of (IMesH)(CI HN)(Cl),Ru=CH brown powder (1.0 gram, 64% yield). CH=C(CH.) 0170 Complex 4 (1.5 grams) was dissolved in toluene 0177 Synthesis of (IMesH)(CHN)(Cl),Ru=CH (10 mL), and 4-phenylpyridine (1.13 grams, 4 mol equiva CH=C(CH.) lents) was added. The reaction flask was purged with argon 0178 Complex 4 (1.5 grams) was dissolved in toluene and the reaction mixture was stirred for approximately 2 (10 mL), and 4-dimethylaminopyridine (0.89 grams, 4 mol hours at about 20° C. to about 25 C. during which time a equivalents) was added. The reaction flask was purged with color change from brown to green was observed. The argon and the reaction mixture was stirred for approximately reaction mixture was transferred into 75 mL of cold (about 2 hours at about 20° C. to about 25 C. during which time 0 C.) pentane, and a green Solid precipitated. The precipi a color change from brown to green was observed. The tate was filtered, washed with 4x20 mL of cold pentane, and reaction mixture was transferred into 75 mL of cold (about dried under WCUU to afford 0 C.) pentane, and a green Solid precipitated. The precipi (IMesH)(C, H.N).(Cl),Ru=CH-CH=C(CH4), 24 as a tate was filtered, washed with 4x20 mL of cold pentane, and green powder (0.9 gram, 58% yield). Synthesis of dried under WCUU to afford (IMesH)(CHN)(Cl),Ru=CH-CH=C(CH) (IMesH)(CHN).(Cl),Ru=CH-CH=C(CH4), 27 as a green powder (0.9 gram, 63% yield). 0171 Complex 4 (1.5 grams) was dissolved in toluene (10 mL), and 4-pyrrolidinopyridine (1.08 grams, 4 mol 0179 H NMR (500 MHz, CDC1): 8 19.10 (d. 111, equivalents) was added. The reaction flask was purged with CH-CH=C(CH), J-11.5 Hz.), 8.18 (br. S, 2H, pyri argon and the reaction mixture was stirred for approximately dine CH), 7.69 (d. 1H, CH-CH=C(CH), J-11.5 Hz), 2 hours at about 20° C. to about 25 C. during which time 7.41 (br. S, 2H, Mes CH), 6.49 (br.s, 2H, pyridine CH), 6.24 a color change from brown to green was observed. The (br. S, 2H, Mes CH), 4.06 (br. m, 4H, NCHCHN), 2.99 (s. US 2003/0069374A1 Apr. 10, 2003 27

6H, pyridine CH-), 2.59 (s, 6H, pyridine CH-), 2.36-2.12 and dried under vacuum to afford 31 as a green powder (2.9 (multiple peaks, 18H, Mes CH), 1.07 (s, 3H, g, 85% yield). Samples for elemental analysis were prepared CH-CH=C(CH)), 1.06 (s, 3H, CH-CH=C(CH)). by recrystallization from CH/pentane followed by drying under Vacuum. These Samples analyze as the monopyridine 0180 Polymerization Example: A 75 gram mass of adduct (IMesH)(CHN)(Cl),Ru=CHPh, probably due to DCPD (containing about 24% trimerized DCPD) was poly loss of pyridine under vacuum. H NMR (CD): & 19.67 (s, merized using (IMesH)(CHN)(Cl),Ru=CH 1H, CHPh), 8.84 (br. S, 2H, pyridine), 8.39 (br. S, 2H, CH=C(CH)=0.0138 grams at a DCPD:Ruratio of (about pyrdine), 8.07 (d. 2H, ortho CH, J–8 Hz), 7.15 (t, 11H, 30,000:1) at a starting temperature of about 24.2 C. para CH, J-7 Hz), 6.83-6.04 (br. multiple peaks, 9H, 0181 Result: Time to reach maximum temperature pyridine, Mes CH), 3.37 (br. d, 4H, CHCH-), 2.79 (br. s. (T)=200 seconds. T=200.9 C. Glass transition tem 6H, Mes CH), 2.45 (br. s. 6H, Mes CH), 2.04 (br. S, 6H, perature measured by therrnal mechanical analysis (TMA)= Mes CH). C{H} NMR (CD): 8314.90 (m, Ru=CHPh), 145 C. Percent residual monomer (toluene extraction at 219.10 (s, Ru-C(N)), 152.94, 150.84, 139.92, 138.38, room temperature)=4.57%. 136.87, 135.99, 134.97, 131.10, 130.11, 129.88, 128.69, 0182 Polymerization Example: A50 gram mass of hexy 123.38, 51.98, 51.37, 21.39, 20.96, 19.32. Anal. Calcd for lnorbornene WS polymerized using CHNC1Ru: C, 61.20; H, 5.76; N, 6.49. Found: C, (IMesH)(CHN)(Cl),Ru=CH-CH=C(CH)= 61.25; H, 5.76; N, 6.58. 0.0074 grams at a HN:Ru ratio of (about 30,000:1) at a 0191 Represententative Synthesis of a Phosphine Com starting temperature of about 16.2 C. plex: IMesH)(PPh)(Cl),Ru=CHPh (41) 0183 Result: Time to reach maximum temperature 0.192 Complex 31 (150 mg, 0.21 mmol) and PPhs (76 (T)=182 seconds. T=141.7 C. mg, 0.28 mmol) were combined in benzene (10 mL) and 0184 Synthesis of (IMesH)(CHN)(Cl),Ru=CH stirred for 10 min. The Solvent was removed under vacuum, and the resulting brown residue was washed with 4x20 mL CH=C(CH.) of pentane and dried in vacuo. Complex 41 was obtained as 0185. Complex 4 (0.5 grams) was dissolved in toluene a brownish powder (125 mg, 73% yield). P{H} NMR (10 mL), and pyridine (10 mL) was added. The reaction flask (CD): 8 37.7 (s). H NMR (C,D): & 19.60 (s, H, was purged with argon and the reaction mixture was Stirred Ru=CHPh), 7.70 (d. 2H, ortho CH, J–8 Hz), 7.29-6.71 for approximately 12 hours at about 20° C. to about 25 C. (multiple peaks, 20H, PPhs, para CH, meta CH, and Mes during which time a color change from brown to brown CH), 6.27 (s, 2H, Mes CH), 3.39 (m, 4H, CHCH), 2.74 (s, green was observed. The reaction mixture was transferred 6H, ortho CH-), 2.34 (s, 6H, ortho CH-), 2.23 (s, 3H, para into 75 mL of cold (about 0°C.) pentane, and a green solid CH), 1.91 (s, 3H, para CH). C{H} NMR (CD): 8 precipitated. The precipitate was filtered, washed with 4x20 305.34 (m, Ru-CHPh), 219.57 (d, Ru-C(N), J =92 mL of cold pen-tane, and dried under Vacuum to afford 28 Hz), 151.69 (d, J =4 Hz), 139.68, 138.35,138.10, 138.97, (IMesH)(CHN)(Cl),Ru=CH-CH=C(CH) as green 137.78, 135.89 135.21, 135.13, 131.96, 131.65, 131.36, crystals (0.2 gram, 47% yield). 130.47, 129.83, 129.59 (d, J=2 Hz), 129.15, 128.92, 0186 H NMR (300 MHz, CDC1): 8 19.19 (d. 11H, 128.68, 128.00, 52.11 (d, Jr=4 Hz), 51.44 (d, Jr=2 Hz), Ru=CH-CH=C(CH), J-10.8 Hz), 8.60-6.85 (mul 21.67, 21.35, 21.04, 19.21. Anal. Calcd for tiple peaks, 15H, pyridine, Mes CH, Ru=CH CH-NCIPRu: C, 66.50; H, 5.70; N, 3.37. Found: C, CH=C(CH), 4.07 (m, 4H, NCHCHN), 2.58-2.27 (mul 66.82; H, 5.76; N, 3.29. tiple peaks, 12H, Mes CH), 2.31 (s, 3H, Mes CH), 2.19 (s, 0193 Synthesis of (IMesH)(OBU),Ru=CHPh (42) 3H, Mes CH), 1.09 (s, 3H, CH-CH=C(CH)), 1.08 (s, 3H, CH-CH=C(CH)). 0194 Complex 31 (7.5 mg, 0.010 mmol) and KO’Bu (3 mg, 0.027 mmol) were combined in CD (0.6 mL) in an 0187 Polymerization Example: A 75 gram mass of NMR tube under nitrogen. The reaction mixture was DCPD (containing about 24% trimerized DCPD) was poly allowed to stand for 15-20 min, during which time a color merized using (IMesH)(CHN)(Cl),Ru=CH change from green to dark red was was observed, and NMR CH=C(CH)=0.0123 grams at a DCPD:Ruratio of (about spectra were recorded after 30 min. H NMR (CD): 8 30,000:1) at a starting temperature of about 12.5° C. 16.56 (s, IH, Ru-CHPh), 7.63 (d. 2H, ortho CH, J=7 0188 Result: Time to reach maximum temperature Hz), 7.2-7.1 (multiple peaks, 3H, meta CH and ortho CH), (T)=129 seconds. T=197.1 C. Glass transition tem 6.97 (s, 4H, Mes CH), 3.43 (s, 4H CHCH-), 2.59 (s, 12H, perature measured by thermal mechanical analysis (TMA) ortho CH-), 2.29 (s, 6H, para CH-), 1.18 (s, 18H, Bu). -157 C. Percent residual monomer (toluene extraction at room temperature)=2.13%. 0195 Synthesis of Tp(IMesH)(Cl)Ru=CHPh (43) 0196) KTp (87 mg, 0.34 mmol) and complex31 (125 mg, 0189 Synthesis of (IMesh)(CHN)(Cl),Ru=CHPh 0.17 mmol) were combined in CHCl (10 mL) and stirred (31) for 1 hour. Pentane (20 mL) was added to precipitate the 0190 Complex 1 (4.0 g, 4.7 mmol) was dissolved in Salts, and the reaction was stirred for an additional 30 min toluene (10 mL), and pyridine (30 mL, 0.37 mol) was added. and then cannula filtered. The resulting bright green Solution The reaction was stirred for 10 min during which time a was concentrated, and the Solid residue was washed with color change from red to bright green was observed. The pentane (2x10 mL) and methanol (2x10 mL) and dried reaction mixture was cannula transferred into 100 mL of under vacuum to afford 43 (84 mg, 66% yield) as an cold (-10 C.) pentane, and a green Solid precipitated. The analytically pure green powder. "H NMR (CDC1): 8 18.73 precipitate was filtered, washed with 4x50 mL of pentane, (s, 1H, Ru-CHPh), 7.87 (d. 1H, Tp, J=2.4 Hz), 7.41 (d. US 2003/0069374A1 Apr. 10, 2003 28

1H, Tp, J-2.1 Hz), 7.35-7.30 (multiple peaks, 3H, Tp and 8.07 (d. 1H, J=11.5 Hz, -CH=), 6.68 (brs, 3H, pyridine), para CH), 7.08 (d. 1 h, Tp, J-1.5 Hz), 6.82 (br. S, 5H, Mes 6.43 (brm, 3H, pyridine), 2.54 (qt, 3H, J=11.5 Hz, PCy), CH, ortho CHand meta CH), 6.24 (br. s. 3H, Mes CH), 6.16 2.27 (d. 6H, J=11.5 Hz, PCy3), 1.91 (qt, 6H, J=12 Hz, (t, 1H, Tp, J-1.8 Hz) 5.95 (d. 1H, Tp, J-1.5 Hz), 5.69 PCy), 1.78 (d. 6H, J=10.5 Hz, PCy), 1.62 (m, 4H, PCy), (t, 1H, Tp, J-2.4 Hz), 5.50 (t, 1H, Tp, J-1.8 Hz), 3.77 1.26 (s, 3H, CH), 1.23 (m, 8H, PCy), 0.75 (s, 3H, CH). (br. d, 4H, CHCH-), 2.91-0893 (br. multiple peaks, 18H, P{H} NMR (121.392 MHz, CD): & 37.17 (s). ortho CH, para CH). C{H} (CDC1): 8 324.29 (m, Ru=CHPh), 220.57 (s, Ru-C(N)), 151.50, 146.08, 0206 Observation of 145.39,142.07, 137.94, 136.57,134.41,133.18, 130.60 (br), (Ph.Tri)(CHN)(Cl),Ru=CH-CH=C(CH) 129.55, 127.98, 106.41, 105.19, 104.51, 53.77 (br), 21.26, 0207 0.020 g of (Ph.Tri)(PCy)(Cl),Ru=CH 20.32 (br). Anal. Calcd for CHNC1BRu: C, 59.56; H, CH=C(CH), 0.020 g of 4-dimethylaminopyridine 5.67; N, 15.02. Found: C, 59.20; H, 5.67; N, 14.72. (excess), and 0.060 mL of CDC1 were added to a screw 0197) Kinetics of the Reaction of 1 with CDN cap NMR tube. The "H NMR spectrum after 2 hours at room 0198 In a cuvette fitted with a rubber septum, a solution temperature showed complete conversion to the desired of 1 (0.88 mM) in toluene (1.6 mL) was prepared. This product (Ph.Tri)(CHN)(Cl),Ru=CH-CH=C(CH). solution was allowed to thermally equilibrate in the UV-vis 0208 H NMR (499,852 MHz, CD): & 18.57 (d. 1H, spectrometer at 20° C. Neat pyridine-d (25-100 pill) was J=13 Hz, Ru-CH), 8.53 (d, J=8 Hz), 7.84 (d, J=6.5 Hz), added via microSyringe, and the reaction kinetics was fol 7.73-6.84 (multiplets), 6.26 (d, J=7 Hz), 6.09 (m), 6.04 (d. lowed by monitoring the disappearance of Starting material J=10.5 Hz), 6.01 (d, J=10.5 Hz), 5.42 (d, J=10.5 Hz), 5.38 (502 nm). For each run, the data were collected over 5 (d, J=17.5 Hz), 3.22 (s), 3.01 (s), 2.99 (s), 1.73 (s), 1.23 (s). half-lives and were fitted to a first-order expoential. Typical R values for the exponential curve fits were greater than 0209 Synthesis of (PCy)(CHN)(Cl),Ru=C=CHPh O.999. 0210 Complex 44 (2.0 grams) was dissolved in toluene 0199 X-ray Crystal Structure of 31 (10 mL), and pyridine (0.9 grams) was added. The reaction 0200 Crystal, intensity collection, and refinement details flask was purged with argon and the reaction mixture was were summarized in Table 1. The selected crystal was stirred for approximately 12 hours at about 20° C. to about mounted on a glass fiber with Paratone-N oil and transferred 25 C. After approximately 12 hours the reaction mixture to a Bruker SMART 1000 CCD area detector equipped with was transferred into 75 mL of cold (about 0°C.) pentane. a Crystal Logic CL24 low-temperature device. Data were The pentane mixture was filtered, washed with 4x20 mL of collected with co-scans at Seven (p values and Subsequently cold pentane, and dried under vacuum to afford processed with SAINT. No absorption or decay corrections (PCy)(CHN)(Cl),Ru=C=CHPh 49 as an orange pow were applied. SHELXTL was used to solve (by direct der (1.5 gram, 88% yield). methods and Subsequent difference Fourier maps) and to refine (full-matrix least-squares on 12),the structure. There Example (1) are two molecules in the asymmetric unit. All non-hydrogen 0211) A 75 gram mass of DCPD (containing about 24% atoms were refined anisotropically; the hydrogen atoms trimerized DCPD) WS polymerized using were placed at calculated positions with UiSO values based (PCy)(CHN)(Cl),Ru=C=CHPh=0.0379 grams at a on the Ueq of the attached atom. Pertinent bond lengths and DCPD:Ruratio of (about 10,000:1) at a starting temperature angles for one molecule are presented in Table 2. of about 81.3 C. Result: Time to reach maximum tempera 0201 Synthesis of (IMes)(CHN)(Cl),Ru=CHPh ture (T)=97 seconds. T=169.1 C. 0202) In a nitrogen filled glovebox, 0.120 g (0.142 mmol) of (IMes)(PCy)C1Ru=CHPh were dissolved in 1 mL of Example (2) pyridine (large excess). The Solution, which turned green 0212. A 75 gram mass of DCPD (containing about 24% immediately, was stirred at room temperature for 30 min trimerized DCPD) WS polymerized using utes. Then 20 mL of hexanes was added, and the flask was (PCy)(CHN)(Cl),Ru=C=CHPh=0.0377 grams in the Stored at -10 C. overnight. The Supernatant was decanted presence of sIMeshCC1=0.0450grams at a DCPD:RuislM from the green precipitate. The precipitate was washed twice esHCClaratio of (about 10,000:1:2) at a starting temperature with 20 mL hexanes and dried under vacuum to obtain 0.080 of about 88.2° C. Result: Time to reach maximum tempera g (78% yield) of the bright green product ture (T)=205 seconds. T=249.7° C. Glass transition (IMes)(py)C1Ru=CHPh. temperature measured by thermal mechanical analysis 0203 H NMR (499.852 MHz, CDC1): 8 19.41 (s, 1H, (TMA)=164.77° C. CHPh), 8.74 (d. 2H, J=7.5 Hz), 7.96 (d. 2H, J=8.5 Hz), 7.70 0213) Synthesis of (d. 2H, J=12.5 Hz), 7.55 (t, 1H, J=12.5 Hz), 7.44 (t, 1H, J=12 (PCy)(CHN)(Cl),Ru=C=CHPh Hz), 7.33 (t, 1H, J=12 Hz), 7.06 (m, 3H), 7.05 (s, 2H), 6.83 (m, 1H), 6.79 (s, 6H), 2.28 (s, 6H, para CH on Mes), 2.22 0214) Complex 44 (2.0 grams) was dissolved in toluene (brs, 12H, ortho CH on Mes). (10 mL), and 4-pyrrolidinopyridine (1.5 grams) was added. 0204 Characterization of The reaction flask was purged with argon and the reaction (PCy)(CHN)(Cl),Ru=CH-CH=C(CH) mixture was stirred for approximately 12 hours at about 20 C. to about 25 C. After approximately 12 hours the reaction 0205 H NMR (499.852 MHz, CD): 8 20.18 (overlap mixture was transferred into 75 mL of cold (about 0° C.) ping dd, 1H, J=10.3 Hz, Ru-CH), 9.14 (brs, 4H, pyridine), pentane. The pentane mixture was filtered, washed with US 2003/0069374A1 Apr. 10, 2003 29

4x20 mL of cold pentane, and dried under vacuum to afford Example (5) (PCy)(CHN)(Cl),Ru=C=CHPh 50 as a light brown powder (1.9 gram, 95% yield). 0223) A 75 g mass of a monomer mixture, prepared by mixing together 37.5 g of DCPD (containing 24 wt % 0215 Synthesis of trimerized DCPD) and 37.5 g of hexylnorbornene, was (PCy)(CHN)(Cl),Ru=C=CHPh polymerized using (PCy)(Cl HN)(Cl),Ru=C=CHPh= 0216 Complex 44 (2.0 grams) was dissolved in toluene 0.0276 g at a DCPD:Ru reactant ratio of (15,000:1) and (10 mL), and 4-dimethylaminopyridine (1.3 grams) was HN:Ru reactant ratio of (15,000:1), by heating the mixture added. The reaction flask was purged with argon and the to a starting temperature of about 80.1° C. Result: Time to reaction mixture was Stirred for approximately 12 hours at reach maximum temperature (T)=195 seconds. T= about 20° C. to about 25 C. After approximately 12 hours 148.8° C. the reaction mixture was transferred into 75 mL of cold (about 0° C.) pentane. The pentane mixture was filtered, Example (6) washed with 4x20 mL of cold pentane, and dried under 0224. A 75 g mass of a monomer mixture, prepared by vacuum to afford (PCy)(CHN)(Cl),Ru=C=CHPh 51 mixing together 37.5 g of DCPD (containing 24 wt % as an orange powder (1.8 gram, 95% yield). trimerized DCPD) and 37.5 g of hexylnorbornene, was 0217 Synthesis of polymerized using (PCy)(CHN)(Cl),Ru=C=CHPh= (PCy)(CHN)(Cl),Ru=C=CHPh 0.0275 g in the presence of S-ImesHCCl=0.0269 g at a DCPD:Ruis-ImesHCC1, reactant ratio of (15,000:1:2) and 0218 Complex 44 (2.0 grams) was dissolved in toluene HN:Ruis-ImesHCC1, reactant ratio of (15,000:1:2), by (10 mL), and 4-phenylpyridine (1.2 grams) was added. The heating the mixture to a starting temperature of about 82.1 reaction flask was purged with argon and the reaction mixture was stirred for approximately 12 hours at about 20 C. Result: Time to reach maximum temperature (T)=180 C. to about 25 C. After approximately 12 hours the reaction seconds. T=217.3 C. mixture was transferred into 75 mL of cold (about 0° C.) 0225 Synthesis of (PCy)(CHN)(Cl),Ru=C=CH pentane. The pentane mixture was filtered, washed with C(CH) 4x20 mL of cold pentane, and dried under vacuum to afford 0226 Complex 45 (2.0 grams) was dissolved in toluene (PCy)(CHN)(Cl),Ru=C=CHPh 52 as an orange pow (10 mL), and pyridine (0.9 grams) was added. The reaction der (0.9 gram, 43% yield). flask was purged with argon and the reaction mixture was stirred for approximately 12 hours at about 20° C. to about Example (1) 25 C. After approximately 12 hours the reaction mixture 0219. A 75 gram mass of DCPD (containing about 24% was transferred into 75 mL of cold (about 0°C.) pentane. trimerized DCPD) was polymerized using (PCy)(C) The pentane mixture was filtered, washed with 4x20 mL of iHN)(Cl),Ru=C=CHPh=0.0455 grams at a DCPD:Ru cold pentane, and dried under vacuum to afford ratio of (about 10,000:1) at a starting temperature of about (PCy)(CHN)-(Cl),Ru=C=CH-C(CH4), 53 as an 79.4° C. Result: Time to reach maximum temperature orange powder (1.5 gram, 88% yield). (T)=90 seconds. T=170.2 C. Example (1) Example (2) 0227. A 75 gram mass of DCPD (containing about 24% 0220) A 75 gram mass of DCPD (containing about 24% trimerized DCPD) WS polymerized using trimerized DCPD) WS polymerized using (PCY)(CHN)(Cl),Ru=C=CH-C(CH)=0.0370 (PCy)(CHN)(Cl),Ru=C=CHPh=0.0451 grams in the grams at a DCPD:Ruratio of (about 10,000:1) at a starting presence of sIMesHCCl=0.0450grams at a DCPD:Ru:sIM temperature of about 79.5 C. Result: Time to reach maxi esHCClaratio of (about 10,000:1:2) at a starting temperature mum temperature (T)=155 seconds. T=207.4 C. of about 82.9° C. Result: Time to reach maximum tempera Glass transition temperature measured by thermal mechani ture (T)=148 seconds. T=242.1 C. Glass transition cal analysis (TMA)=70.73 C. temperature measured by thermal mechanical analysis (TMA)=158.28° C. Example (2) Example (3) 0228) A 75 gram mass of DCPD (containing about 24% 0221) A 75 g mass of hexylnorbornene was polymerized trimerized DCPD) WS polymerized using using (PCy)(CHN)-(Cl),Ru=C=CHPh=0.0244 g at a (PCy)(CHN)(Cl),Ru=C=CH-C(CH)=0.0368 grams in the presence of SIMeshCCl=0.0446 grams at a HN:Ru reactant ratio of (15,000:1) at a starting temperature DCPD:RuislMesHCC1, ratio of (about 10,000:1:2) at a start of about 80.1° C. Result: Time to reach maximum tempera ing temperature of about 82.2 C. Result: Time to reach ture (T)=391 seconds. T=155.4 C. maximum temperature (T)=76 seconds. T=239.7 C. Example (4) Glass transition temperature measured by thermal mechani cal analysis (TMA)=178.83° C. 0222. A 75 g mass of hexylnorbornene, was polymerized using (PCy)(CHN)(Cl),Ru=C=CHPh=0.0246 g in Example (3) the presence of s-ImesHCCls=0.0240 g at a HN:Ruis ImesHCCl reactant ratio of (15,000:1:2) at a starting tem 0229. A 75 g mass of hexylnorbornene was polymerized perature of about 81.7 C. Result: Time to reach maximum using (PCy)(CHN)(Cl),Ru=C=CH-C(CH)= temperature (T)=224 Seconds. T=193.9 C. 0.0148 g at a HN:Ru reactant ratio of (20,000:1) at a US 2003/0069374A1 Apr. 10, 2003 30 starting temperature of about 82.4° C. Result: Time to reach mum temperature (T)=244 seconds. T=230.0 C. maximum temperature (T)=212 seconds. T=189.4 C. Glass transition temperature measured by thermal mechani cal analysis (TMA)=126.338 C. Example (4) 0230. A 75 g mass of hexylnorbornene, was polymerized 0237) Synthesis of using (PCy)(CHN)(Cl),Ru=C=CH-C(CH)= (PCy3)(CHN)(Cl),Ru=C=CHPh 0.0149 g in the presence of S-ImesHCCl=0.0092 g at a 0238 Complex 44 (2.0 grams) was dissolved in toluene HN:Ruis-ImesHCC1, reactant ratio of (20,000:1:1) at a (10 mL), and 1,10-phenanthroline (0.9 grams) was added. starting temperature of 80.9 C. Result: Time to reach The reaction flask waspurged with argon and the reaction maximum temperature (T)=154 seconds. T=194.5 C. mixture was stirred for approximately 12 hours at about 20 C. to about 25 C. After approximately 12 hours the reaction Example (5) mixture was transferred into 75 mL of cold (about 0° C.) 0231. A 75 g mass of a monomer mixture, prepared by pentane. The pentane mixture was filtered, washed with mixing together 37.5 g of DCPD (containing 24 wt % 4x20 mL of cold pentane, and dried under vacuum to afford trimerized DCPD) and 37.5 g of hexylnorbornene, was (PCy)(CHN)(Cl),Ru=C=CHPh 55 as an orange polymerized using (PCy)(CHN)(Cl),Ru=C=CH powder (1.7 gram, 94% yield). C(CH)=0.0163 g at a DCPD:Ru reactant ratio of (20, 000:1) and HN:Ru reactant ratio of (20,000:1), by heating 0239 H NMR (500 MHz, CDC1): 8=6.98-10.18 (mul the mixture to a starting temperature of about 82.3 C. tiple peaks, 13H), 5.03 (d. 1H, J=4 Hz, vinylidene peak), Result: Time to reach maximum temperature (T)=149 0.95-2.70 (multiple peaks, 33H) ppm. seconds. T=191.5 C. 0240 Synthesis of (PCy)(CHN)(Cl),Ru=C=CHPh Example (6) 0241 Complex 44 (2.0 grams) was dissolved in toluene 0232 A 75 g mass of a monomer mixture, prepared by (10 mL), and 2,2'-bipyridine (0.8 grams) was added. The mixing together 37.5 g of DCPD (containing 24 wt % reaction flask was purged with argon and the reaction trimerized DCPD) and 37.5 g of hexylnorbornene, was mixture was stirred for approximately 12 hours at about 20 polymerized using (PCy)(CHN)(Cl),Ru=C=CH C. to about 25 C. After approximately 12 hours the reaction C(CH)=0.0163 g in the presence of S-ImesHCCl=0.0100 mixture was transferred into 75 mL of cold (about 0° C.) g at a DCPD:Ru:s-ImesHCCls reactant ratio of (20,000:1:2) pentane. The pentane mixture was filtered, washed with and H.N:Ru:s-ImesHCCls reactant ratio of (20,000:1:2), by 4x20 mL of cold pentane, and dried under vacuum to afford heating the mixture to a starting temperature of about 81.2 (PCy)(CHN)(Cl),Ru=C=CHPh 56 as a green powder C. Result: Time to reach maximum temperature (T)=169 (1.6 gram, 94% yield). Seconds. T=221.3 C. 0233 Synthesis of 0242 Synthesis of (PCy)(CiOH8N)(Cl),Ru=C=CHPh (PCy)(CHN)(Cl),Ru=C=CHPh 0234 Complex 44 (2.0 grams) was dissolved in toluene 0243 Complex 44 (2.0 grams) was dissolved in toluene (10 mL), and 4,4'-bipyridine (1.5 grams) was added. The (10 mL), and 2,2'-biquinoline (1.2 grams) was added. The reaction flask was purged with argon and the reaction reaction flask was purged with argon and the reaction mixture was stirred for approximately 12 hours at about 20 mixture was stirred for approximately 12 hours at about 20 C. to about 25 C. After approximately 12 hours the reaction C. to about 25 C. After approximately 12 hours the reaction mixture was transferred into 75 mL of cold (about 0° C.) mixture was transferred into 75 mL of cold (about 0° C.) pentane. The pentane mixture was filtered, washed with pentane. The pentane mixture was filtered, washed with 4x20 mL of cold pentane, and dried under vacuum to afford 4x20 mL of cold pentane, and dried under vacuum to afford (PCy)(CHN)(Cl),Ru=C=CHPh 54 as an orange (PCy)(C.HN)(Cl),Ru=C=CHPh 57 as a purple powder (1.9 gram, 90% yield). powder (1.7 gram, 89% yield). Example (1) 0244 H NMR (300 MHz, CD): 86.88-9.15 (multiple peaks, 17H), 4.79 (d. 1H, J=3 Hz, vinylidene), 1.21-2.86 0235 A 75 gram mass of DCPD (containing about 24% (multiple peaks, 33H) ppm. trimerized DCPD) WS polymerized using (PCy)(CioH8N)(Cl),Ru=C=CHPh=0.0457 grams at a 0245 Synthesis of DCPD:Ruratio of (about 10,000:1) at a starting temperature (PCy)(CHN)(Cl),Ru=C=CH-C(CH) of about 82.7 C. Result: Time to reach maximum tempera 0246 Complex 45 (2.0 grams) was dissolved in toluene ture (T)=246 Seconds. T=159.9 C. (10 mL), and 4-pyrrolidinopyridine (1.5 grams) was added. Example (2) The reaction flask was purged with argon and the reaction mixture was stirred for approximately 12 hours at about 20 0236 A 75 gram mass of DCPD (containing about 24% C. to about 25 C. After approximately 12 hours the reaction trimerized DCPD) WS polymerized using mixture was transferred into 75 mL of cold (about 0° C.) (PCy)(CHN)(Cl),Ru=C=CHPh=0.0462 grams in pentane. The pentane mixture was filtered, washed with the presence of SIMesHCCl=0.0448 grams at a DCP 4x20 mL of cold pentane, and dried under vacuum to afford D:Ru:sIMeshCCI ratio of (about 10,000:1:2) at a starting (PCy)(CHN)(Cl),Ru=C=CH-C(CH-) 58 as a temperature of about 82.3 C. Result: Time to reach maxi dark green powder (1.8 gram, 90% yield). US 2003/0069374A1 Apr. 10, 2003

0247 Synthesis of grams in the presence of SIMeshCCl=0.0449 grams at a (PCy)(CHN)(Cl),Ru=C=CH-C(CH) DCPD:RuislMesHCC1, ratio of (about 10,000:1:2) at a start 0248 Complex 45 (2.0 grams) was dissolved in toluene ing temperature of about 81.1 C. Result: Time to reach (10 mL), and 4,4'-bipyridine (1.5 grams) was added. The maximum temperature (T)=126 Seconds. T=246.2 C. reaction flask was purged with argon and the reaction Glass transition temperature measured by thermal mechani mixture was stirred for approximately 12 hours at about 20 cal analysis (TMA)=175.35° C. C. to about 25 C. After approximately 12 hours the reaction 0256 Synthesis of mixture was transferred into 75 mL of cold (about 0° C.) (PCy)(CHN)(Cl),Ru=C=CH-C(CH) pentane. The pentane mixture was filtered, washed with 0257 Complex 45 (2.0 grams) was dissolved in toluene 4x20 mL of cold pentane, and dried under vacuum to afford (10 mL), and 1,10-phenanthroline (0.9 grams) was added. (PCy)(CHN)(Cl),Ru=C=CH-C(CH-) 59 as a The reaction flask was purged with argon and the reaction brown powder (1.7 gram, 81% yield). mixture was stirred for approximately 12 hours at about 20 C. to about 25 C. After approximately 12 hours the reaction Example (1) mixture was transferred into 75 mL of cold (about 0° C.) 0249. A 75 gram mass of DCPD (containing about 24% pentane. The pentane mixture was filtered, washed with trimerized DCPD) WS polymerized using 4x20 mL of cold pentane, and dried under vacuum to afford (PCy)(CHN)(Cl),Ru=C=CH-C(CH)=0.0451 (PCy)(CHN)(Cl),Ru=C=CH-C(CH), 61 as an grams at a DCPD:Ruratio of (about 10,000:1) at a starting orange powder (1.5 gram, 83% yield). temperature of about 81.2 C. Result: Time to reach maxi 0258 H NMR (300 MHz, CD): 8=6.90-10.73 (mul mum temperature (T)=349 seconds. T=157.7 C. tiple peaks, 8H), 4.02 (d. 1H, J=3 Hz, vinylidene), 1.46-3.06 Example (2) (multiple peaks, 33H), 1.62 (s, 9H) ppm. 0259 Synthesis of 0250) A 75 gram mass of DCPD (containing about 24% (PCy)(CiOH8N)(Cl),Ru=C=CH-C(CH4), Complex trimerized DCPD) WS polymerized using 45 (2.0 grams) was dissolved in toluene (10 mL), and (PCy)(CHN)(Cl),Ru=C=CH-C(CH)=0.0447 2,2'-bipyridine (0.8 grams) was added. The reaction flask grams in the presence of SIMesHCCl=0.0445 grams at a was purged with argon and the reaction mixture was Stirred DCPD:RussiMeshCC1, ratio of (about 10,000:1:2) at a start for approximately 12 hours at about 20° C. to about 25 C. ing temperature of about 80.8 C. Result: Time to reach After approximately 12 hours the reaction mixture was maximum temperature (T)=189 seconds. T=208.4°C. transferred into 75 mL of cold (about 0°C.) pentane. The Glass transition temperature measured by thermal mechani pentane mixture was filtered, washed with 4x20 mL of cold cal analysis (TMA)=95.70° C. pentane, and dried under Vacuum to afford 0251 Synthesis of (PCy)(CHN)(Cl),Ru=C=CH-C(CH4), 62 as an (PCy)(CHN)(Cl),Ru=C=CH-C(CH) orange powder (1.3 gram, 76% yield). 0252 Complex 45 (2.0 grams) was dissolved in toluene 0260 Synthesis of (10 mL), and 4-phenylpyridine (1.6 grams) was added. The (PCy)(CHN)(Cl),Ru=C=CH-C(CH) reaction flask was purged with argon and the reaction 0261 Complex 45 (2.0 grams) was dissolved in toluene mixture was stirred for approximately 12 hours at about 20 (10 mL), and 2,2'-biquinoline (1.3 grams) was added. The C. to about 25 C. After approximately 12 hours the reaction reaction flask was purged with argon and the reaction mixture was transferred into 75 mL of cold (about 0° C.) mixture was stirred for approximately 12 hours at about 20 pentane. The pentane mixture was filtered, washed with C. to about 25 C. After approximately 12 hours the reaction 4x20 mL of cold pentane, and dried under vacuum to afford mixture was transferred into 75 mL of cold (about 0° C.) (PCy)(CHN)(Cl),Ru=C=CH-C(CH) 60 as a pentane. The pentane mixture was filtered, washed with brown powder (1.7 gram, 81% yield). 4x20 mL of cold pentane, and dried under vacuum to afford (PCy)(CHN)(Cl),Ru=C=CH-C(CH) 63 as a 0253) H NMR (300 MHz, CD): 8=6.89-10.08 (mul gray powder (1.1 gram, 58% yield). tiple peaks, 18H), 4.17 (d. 1H, J=4 Hz, vinylidene), 1.25 2.74 (multiple peaks, 33H), 1.31 (s, 9H) ppm. 0262 Synthesis of (IMesH)(CHN)(Cl),Ru=C=CH-C(CH) Example (1) 0263 Complex 46 (2.0 grams) was dissolved in toluene 0254) A 75 gram mass of DCPD (containing about 24% (10 mL), and 4-pyrrolidinopyridine (1.4 grams) was added. trimerized DCPD) was polymerized using (PCy)(Cl The reaction flask was purged with argon and the reaction lHN)(Cl),Ru=C=CH-C(CH)=0.0443 grams at a mixture was stirred for approximately 12 hours at about 20 DCPD:Ruratio of (about 10,000:1) at a starting temperature C. to about 25 C. After approximately 12 hours the reaction of about 82.0° C. Result: Time to reach maximum tempera mixture was transferred into 75 mL of cold (about 0° C.) ture (T)=208 seconds. T=205.1 C. Glass transition pentane. The pentane mixture was filtered, washed with temperature measured by thermal mechanical analysis 4x20 mL of cold pentane, and dried under vacuum to afford (IMesH)(CHN)(Cl),Ru=C=CH-C(CH) 64 as a (TMA)=54.42° C. gray powder (0.7 gram, 35% yield). Example (2) Example (1) 0255. A 75 gram mass of DCPD (containing about 24% 0264. A 75 gram mass of DCPD (containing about 24% trimerized DCPD) WS polymerized using trimerized DCPD) WS polymerized using (PCy)(CHN)(Cl),Ru=C=CH-C(CH)=0.0445 (IMesH)(CHN)(Cl),Ru=C=CH-C(CH)=0.0456 US 2003/0069374A1 Apr. 10, 2003 32 grams at a DCPD:Ruratio of (about 10,000:1) at a starting 0273 Synthesis of temperature of about 80.7 C. Result: Time to reach maxi (IMesH)(CHN)(Cl),Ru=C=CH-C(CH) mum temperature (T)=143 seconds. T=170.5 C. 0274 Complex 46 (2.0 grams) was dissolved in toluene 0265 Synthesis of (10 mL), and 2,2'-bipyridine (0.8 grams) was added. The reaction flask was purged with argon and the reaction (IMesH)(CHN)(Cl),Ru=C=CH-C(CH) mixture was stirred for approximately 12 hours at about 20 0266 Complex 46 (2.0 grams) was dissolved in toluene C. to about 25 C. After approximately 12 hours the reaction (10 mL), and 4,4'-bipyridine (1.5 grams) was added. The mixture was transferred into 75 mL of cold (about 0° C.) reaction flask was purged with argon and the reaction pentane. The pentane mixture was filtered, washed with mixture was stirred for approximately 12 hours at about 20 4x20 mL of cold pentane, and dried under vacuum to afford C. to about 25 C. After approximately 12 hours the reaction (IMesH)(CHN)(C1)-Ru=C=CH-C(CH), 68 as a mixture was transferred into 75 mL of cold (about 0° C.) brown powder (0.9 gram, 53% yield). pentane. The pentane mixture was filtered, washed with 0275 Synthesis of (PCy)(CHN)(Cl),Ru=C=C= 4x20 mL of cold pentane, and dried under vacuum to afford C(Ph), (IMesH)(CHN)(Cl),Ru=C=CH-C(CH) 65 as a 0276 Complex 47 (2.0 grams) was dissolved in toluene dark purple powder (2.0 gram, 95% yield). (10 mL), and pyridine (0.7 grams) was added. The reaction flask was purged with argon and the reaction mixture was Example (1) stirred for approximately 12 hours at about 20° C. to about 25 C. After approximately 12 hours the reaction mixture 0267 A 75 g mass of hexylnorbornene was polymerized was transferred into 75 mL of cold (about 0°C.) pentane. using (IMesH)(CHN)(Cl),Ru=C=CH-C(CH)= The pentane mixture was filtered, washed with 4x20 mL of 0.0488 g at a HN:Ru reactant ratio of (7,500:1) at a starting cold pentane, and dried under vacuum to afford temperature of about 80.6 C. Result: Time to reach maxi (PCy)(CHN)-(Cl),Ru=C=C=C(Ph), 69 as a brown mum temperature (T)=183 seconds. T=191.7 C. powder (0.7 gram, 41% yield). 0277 Synthesis of Example (2) (PCy)(CHN)(Cl),Ru=C=CH-C(CH) 0268 A 75 g mass of a monomer mixture, prepared by 0278 Complex 45 (2.0 grams) was dissolved in toluene mixing together 37.5 g of DCPD (containing 24 wt % (10 mL), and 4-dimethylaminopyridine (1.2 grams) was trimerized DCPD) and 37.5 g of hexylnorbornene, was added. The reaction flask was purged with argon and the polymerized using reaction mixture was Stirred for approximately 12 hours at (IMesH)(CHN)(Cl),Ru=C=CH-C(CH)=0.0549 about 20° C. to about 25 C. After approximately 12 hours g at a DCPD:Ru reactant ratio of (7,500:1) and HN:Ru the reaction mixture was transferred into 75 mL of cold reactant ratio of (7,500:1), by heating the mixture to a (about 0° C.) pentane. The pentane mixture was filtered, starting temperature of about 80.3 C. Result: Time to reach washed with 4x20 mL of cold pentane, and dried under maximum temperature (T)=138 seconds. T=181.9 C. vacuum to afford (PCy)(C, HoN)-(Cl),Ru=C=CH C(CH) 70 as pink powder (1.6 gram, 84% yield). 0269. Synthesis of 0279 H NMR (300 MHz, CD): 8–5.89-9.66 (multiple (IMesH)(CHN)(Cl),Ru=C=CH-C(CH) peaks, 8H), 4.14 (d, J=4 Hz, vinylidene), 1.31-2.78 (multiple 0270 Complex 46 (2.0 grams) was dissolved in toluene peaks, 45H), 1.40 (s, 9H) ppm. (10 mL), and 4-phenylpyridine (1.5 grams) was added. The reaction flask was purged with argon and the reaction Example (1) mixture was stirred for approximately 12 hours at about 20 C. to about 25 C. After approximately 12 hours the reaction 0280 A 75 gram mass of DCPD (containing about 24% mixture was transferred into 75 mL of cold (about 0° C.) trimerized DCPD) WS polymerized using pentane. The pentane mixture was filtered, washed with (PCy)(CHN)(Cl),Ru=C=CH-C(CH)=0.0410 4x20 mL of cold pentane, and dried under vacuum to afford grams at a DCPD:Ruratio of (about 10,000:1) at a starting (IMesH)(CHN)(Cl),Ru=C=CH-C(CH2) 66 as a temperature of about 81.2 C. Result: Time to reach maxi light brown powder (0.6 gram, 29% yield). mum temperature (T)=306 seconds. T=189.6 C. Glass transition temperature measured by thermal mechani 0271 Synthesis of cal analysis (TMA)=35.88 C. (IMesH)(CHN)(Cl),Ru=C=CH-C(CH) Example (2) 0272 Complex 46 (2.0 grams) was dissolved in toluene (10 mL), and pyridine (0.8 grams) was added. The reaction 0281) A 75 gram mass of DCPD (containing about 24% flask was purged with argon and the reaction mixture was trimerized DCPD) WS polymerized using stirred for approximately 12 hours at about 20° C. to about (PCy)(CHN)(Cl),Ru=C=CH-C(CH)=0.0411 25 C. After approximately 12 hours the reaction mixture grams in the presence of SIMeshCCl=0.0450 grams at a was transferred into 75 mL of cold (about 0°C.) pentane. DCPD:RuislMesHCC1, ratio of (about 10,000:1:2) at a start The pentane mixture was filtered, washed with 4x20 mL of ing temperature of about 81.9 C. Result: Time to reach cold pentane, and dried under vacuum to afford maximum temperature (Tman)=161 seconds. T=246.5 (IMesH)(CHN)-(Cl),Ru=C=CH-COCH4), 67 as a yel C. Glass transition temperature measured by thermal low powder (0.9 gram, 53% yield). mechanical analysis (TMA)=169.56° C. US 2003/0069374A1 Apr. 10, 2003

0282) Synthesis of Example (2) (IMesH)(CHN)(Cl),Ru=C=CH-C(CH) 0291. A 75 g mass of hexylnorbornene was polymerized 0283 Complex 46 (2.0 grams) was dissolved in toluene using (PCy)(CHN)(Cl),Ru=C=C=C(Ph)=0.0536 g (10 mL), and 4-dimethylaminopyridine (1.2 grams) was in the presence of S-ImesHCCl=0.0478 g at a H.N:Ru:s- added. The reaction flask was purged with argon and the ImesHCCls reactant ratio of (7,500:1:2) at a starting tem reaction mixture was Stirred for approximately 12 hours at perature of 80.3 C. Result: Time to reach maximum tem about 20° C. to about 25 C. After approximately 12 hours perature (T)=230 seconds. T=195.6 C. the reaction mixture was transferred into 75 mL of cold Example (3) (about 0° C.) pentane. The pentane mixture was filtered, 0292 A 75 g mass of a monomer mixture, prepared by washed with 4x20 mL of cold pentane, and dried under mixing together 37.5 g of DCPD (containing 24 wt % vacuum to afford (IMesH)(C,HoN).(Cl),Ru=C=CH trimerized DCPD) and 37.5 g of hexylnorbornene, was C(CH) 71 as a gray powder (0.9 gram, 47% yield). polymerized using (PCy)(CHN)(Cl),Ru=C=C= 0284) Synthesis of (PCy)(CHN)(Cl),Ru=C=C= C(Ph)=0.0599 g in the presence of s-ImesHCCl=0.0536 g at a DCPD:Ru:S-ImesHCC1, reactant ratio of (7,500:1:2) C(Ph), and H.N:Ru:s-ImesHCCl reactant ratio of (7,500:1:2), by 0285 Complex 47 (2.0 grams) was dissolved in toluene heating the mixture to a starting temperature of about 82.4 (10 mL), and 4-dimethylaminopyridine (1.1 grams) was C. Result: Time to reach maximum temperature (T)=178 added. The reaction flask was purged with argon and the seconds. T=220.8 C. reaction mixture was Stirred for approximately 12 hours at 0293) Synthesis of (PCy)(CHN)(Cl),Ru=C=C= about 20° C. to about 25 C. After approximately 12 hours the reaction mixture was transferred into 75 mL of cold C(Ph), (about 0° C.) pentane. The pentane mixture was filtered, 0294 Complex 47 (2.0 grams) was dissolved in toluene washed with 4x20 mL of cold pentane, and dried under (10 mL), and 4,4'-bipyridine (1.4 grams) was added. The vacuum to afford (PCy)(C,HoN)-(Cl),Ru=C=C= reaction flask was purged with argon and the reaction C(Ph) 72 as a brown powder (1.3 gram, 68% yield). mixture was stirred for approximately 12 hours at about 20 C. to about 25 C. After approximately 12 hours the reaction 0286) Synthesis of (PCy)(CHSN)(Cl),Ru=C=C= mixture was transferred into 75 mL of cold (about 0° C.) C(Ph), pentane. The pentane mixture was filtered, washed with 4x20 mL of cold pentane, and dried under vacuum to afford 0287 Complex 47 (2.0 grams) was dissolved in toluene (PCy)(CHN)(Cl),Ru=C=C=C(Ph) 75 as a red (10 mL), and 1,10-phenanthroline (0.8 grams) was added. brown powder (2.0 gram, 95% yield). The reaction flask was purged with argon and the reaction mixture was stirred for approximately 12 hours at about 20 Example (1) C. to about 25 C. After approximately 12 hours the reaction 0295) A 75 gram mass of DCPD (containing about 24% mixture was transferred into 75 mL of cold (about 0° C.) trimerized DCPD) WS polymerized using pentane. The pentane mixture was filtered, washed with (PCy)(CHN)(Cl),Ru=C=C=C(Ph)=0.0500 grams 4x20 mL of cold pentane, and dried under vacuum to afford in the presence of SIMeshCCl=0.0448 grams at a DCP (PCy)(CHN)(Cl),Ru=C=C=C(Ph) 73 as a red D:Ru:SIMeshCCI ratio of (about 10,000:1:2) at a starting brown powder (1.2 gram, 67% yield). temperature of about 84.6 C. Result: Time to reach maxi mum temperature (T)=190 seconds. T=224.7 C. 0288 Synthesis of (PCy)(CHN)(Cl),Ru=C=C= Glass transition temperature measured by thermal mechani C(Ph), cal analysis (TMA)= 105.52° C. 0289 Complex 47 (2.0 grams) was dissolved in toluene 0296 Synthesis of (PCy)(CHN)(Cl),Ru=C=C= (10 mL), and 4-phenylpyridine (1.4 grams) was added. The C(Ph), reaction flask was purged with argon and the reaction 0297 Complex 47 (2.0 grams) was dissolved in toluene mixture was stirred for approximately 12 hours at about 20 (10 mL), and 4-pyrrolidinopyridine (1.3 grams) was added. C. to about 25 C. After approximately 12 hours the reaction The reaction flask was purged with argon and the reaction mixture was transferred into 75 mL of cold (about 0° C.) mixture was stirred for approximately 12 hours at about 20 pentane. The pentane mixture was filtered, washed with C. to about 25 C. After approximately 12 hours the reaction 4x20 mL of cold pentane, and dried under vacuum to afford mixture was transferred into 75 mL of cold (about 0° C.) (PCy)(C IHN)(Cl),Ru=C=C=C(Ph) 74 as a dark pentane. The pentane mixture was filtered, washed with purple powder (1.5 gram, 71% yield). 4x20 mL of cold pentane, and dried under vacuum to afford (PCy)(CHN)(Cl),Ru=C=C=C(Ph) 76 as a dark Example (1) purple powder (1.4 gram, 70% yield). 0290. A 75 gram mass of DCPD (containing about 24% 0298 Synthesis of (PCy)(CioH8N)(Cl),Ru=C=C= trimerized DCPD) WS polymerized using C(Ph), (PCy)(CHN)(Cl),Ru=C=C=C(Ph)=0.0499 grams in 0299 Complex 47 (2.0 grams) was dissolved in toluene the presence of SIMesHCCl=0.0447 grams at a DCP (10 mL), and 2,2'-bipyridine (0.7 grams) was added. The D:Ru:sIMeshCCI ratio of (about 10,000:1:2) at a starting reaction flask was purged with argon and the reaction temperature of about 83.8 C. Result: Time to reach maxi mixture was stirred for approximately 12 hours at about 20 mum temperature (T)=288 seconds. T=238.7 C. C. to about 25 C. After approximately 12 hours the reaction Glass transition temperature measured by thermal mechani mixture was transferred into 75 mL of cold (about 0° C.) cal analysis (TMA)=124.72° C. pentane. The pentane mixture was filtered, washed with US 2003/0069374A1 Apr. 10, 2003 34

4x20 mL of cold pentane, and dried under vacuum to afford D:Ruratio of (about 10,000:1) at a starting temperature of (PCy)(CHN)(Cl),Ru=C=C=C(Ph). 77 as a dark about 80.9 C. Result: Time to reach maximum temperature purple powder (1.1 gram, 65% yield). (T)=275 seconds. T=118.2 C. 0300 Synthesis of (IMesH)(CHN)(Cl),Ru=C=C= 0310. Synthesis of C(Ph), (IMesH)(CIIoHN)(Cl),Ru=C=C=C(Ph). 0301 Complex 48 (2.0 grams) was dissolved in toluene (10 mL), and pyridine (0.7 grams) was added. The reaction 0311 Complex 48 (2.0 grams) was dissolved in toluene flask was purged with argon and the reaction mixture was (10 mL), and 4,4'-bipyridine (1.3 grams) was added. The stirred for approximately 12 hours at about 20° C. to about reaction flask was purged with argon and the reaction 25 C. After approximately 12 hours the reaction mixture mixture was stirred for approximately 12 hours at about 20 was transferred into 75 mL of cold (about 0°C.) pentane. C. to about 25 C. After approximately 12 hours the reaction The pentane mixture was filtered, washed with 4x20 mL of mixture was transferred into 75 mL of cold (about 0° C.) cold pentane, and dried under vacuum to afford pentane. The pentane mixture was filtered, washed with (IMesH)(CHN)-(Cl),Ru=C=C=C(Ph), 78 as a red 4x20 mL of cold pentane, and dried under vacuum to afford brown powder (0.9 gram, 53% yield). (IMesH)(CHN)(Cl),Ru=C=C=C(Ph) 82 as a brown 0302) H NMR (300 MHz, CD): 8=6.52-8.09 (multiple powder (1.9 gram, 90% yield). peaks, 20H), 4.00 (s, 4H, sIMes)1.00-2.28 (multiple peaks, 18H) ppm. Example (1) 0303 Synthesis of 0312. A 75 gram mass of DCPD (containing about 24% (IMesH)(CHN)(Cl),Ru=C=C=C(Ph). trimerized DCPD) WS polymerized using 0304 Complex 48 (2.0 grams) was dissolved in toluene (IMesH)(CHN)(Cl),Ru=C=C=C(Ph)=0.0512 (10 mL), and 4-dimethylaminopyridine (1.0 grams) was grams at a DCPD:Ruratio of (about 10,000:1) at a starting added. The reaction flask was purged with argon and the temperature of about 80.1° C. Result: Time to reach maxi reaction mixture was Stirred for approximately 12 hours at mum temperature (T)=144 seconds. T=138.8 C. about 20° C. to about 25 C. After approximately 12 hours the reaction mixture was transferred into 75 mL of cold Example (2) (about 0° C.) pentane. The pentane mixture was filtered, washed with 4x20 mL of cold pentane, and dried under 0313 A 75 g mass of hexylnorbornene was polymerized vacuum to afford (IMesH)(C, HoN)-(Cl),Ru=C=C= using (IMesH)(CHN)(Cl),Ru=C=C=C(Ph)= C(Ph) 79 as a red-brown powder (1.0 gram, 53% yield). 0.0552 g at a HN:Ru reactant ratio of (7,500:1) at a starting temperature of about 80.3 C. Result: Time to reach maxi 0305 Synthesis of (IMesH)(CHN)(Cl),Ru=C=C= mum temperature (T)=578 seconds. T=138.5 C. C(Ph), 0306 Complex 48 (2.0 grams) was dissolved in toluene Example (3) (10 mL), and 1,10-phenanthroline (0.8 grams) was added. The reaction flask was purged with argon and the reaction 0314. A 75 g mass of a monomer mixture, prepared by mixture was stirred for approximately 12 hours at about 20 mixing together 37.5 g of DCPD (containing 24 wt % C. to about 25 C. After approximately 12 hours the reaction trimerized DCPD) and 37.5 g of hexylnorbornene, was mixture was transferred into 75 mL of cold (about 0° C.) polymerized using (IMesh)(CHN)(Cl),Ru=C=C= pentane. The pentane mixture was filtered, washed with C(Ph)=0.0617 g at a DCPD:Ru reactant ratio of (7,500:1) 4x20 mL of cold pentane, and dried under vacuum to afford and HN:Ru reactant ratio of (7,500:1), by heating the (IMesH)(CHN)(Cl),Ru=C=C=C(Ph) 80 as a red mixture to a starting temperature of about 80.6 C. Result: powder (0.6 gram, 33% yield). Time to reach maximum temperature (T)=259 seconds. 0307 Synthesis of (IMesH)(CHN)(Cl),Ru=C=C= T=135.7° C. C(Ph), 0315 Synthesis of (IMesH)(CHN)(Cl),Ru=C=C= 0308 Complex 48 (2.0 grams) was dissolved in toluene C(Ph), (10 mL), and 4-phenylpyridine (1.3 grams) was added. The reaction flask was purged with argon and the reaction 0316 Complex 48 (2.0 grams) was dissolved in toluene mixture was stirred for approximately 12 hours at about 20 (10 mL), and 2,2'-bipyridine (0.7 grams) was added. The C. to about 25 C. After approximately 12 hours the reaction reaction flask was purged with argon and the reaction mixture was transferred into 75 mL of cold (about 0° C.) mixture was stirred for approximately 12 hours at about 20 pentane. The pentane mixture was filtered, washed with C. to about 25 C. After approximately 12 hours the reaction 4x20 mL of cold pentane, and dried under vacuum to afford mixture was transferred into 75 mL of cold (about 0° C.) (IMesH)(CHN)(Cl),Ru=C=C=C(Ph) 81 as a brown pentane. The pentane mixture was filtered, washed with powder (1.1 gram, 52% yield). 4x20 mL of cold pentane, and dried under vacuum to afford (IMesH)(CHN)(Cl),Ru=C=C=C(Ph) 83 as a red Example (1) brown powder (1.3 gram, 76% yield). 0309. A 75 gram mass of DCPD (containing about 24% 0317 H NMR (300 MHz, CD): 8=6.60-7.85 (multiple trimerized DCPD) was polymerized using (IMesH)(Cl peaks, 18H), 4.00 (s, 4H, sIMes)1.08-2.60 (multiple peaks, HoN)(Cl),Ru=C=C=C(Ph)=0.0515 grams at a DCP 18H) ppm. US 2003/0069374A1 Apr. 10, 2003 35

What is claimed is: 11. The compound of claim 1 wherein L, L'and L are 1. A compound of the formula: each independently Selected from the group consisting of a monodentate, bidentate or tetradentate neutral electron donor ligand. L R1 L R1 Xz. M Xz. M 12. The compound of claim 11 wherein L, L'and L are each independently Selected from the group consisting of L'--1. O L'-' (-C=1. X R X R phosphine, Sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, Stibine, ether, amine, amide, imine, Sulfoxide, carboxyl, nitrosyl, pyridine, and thioether, N-het wherein erocyclic carbene ligand or any derivatives therefrom. M is ruthenium or osmium; 13. The compound of claim 1 wherein both L'and L are X and X’ are the same or different and are each indepen either the same or different N-heterocyclic carbene ligands. dently any anionic ligand; 14. The compound of claim 1 wherein the N-heterocyclic L., L', and L are the same or different and are each carbene ligand is Selected from the group consisting of: independently any neutral electron donor ligand; R and R' are the same or different and are each indepen R6 R7 R6 R. R. R7 dently hydrogen or a Substituted or unsubstituted Sub Stituent Selected from the group consisting of C-Co alkyl, C-Co alkenyl, C-Co alkynyl, aryl, C-Co R10-N N-R11 R10-N N-R11 carboxylate, C-Co alkoxy, C2-Coalkenyloxy, C2-Co N1 N1 alkynyloxy, aryloxy, C-Co alkoxycarbonyl, C-Co OO OO alkylthio, C-C alkylsulfonyl, C-C alkylsulfinyl, R7 and silyl. NS 2. The compound of claim 1 wherein at least one of the R and R' substituent group is substituted with one or more R- N-R 11 moieties Selected from the group consisting of C-C alkyl, N1 C-Co alkoxy, and aryl, and wherein the moiety is Substi tuted or unsubstituted. 3. The compound of claim 2 wherein the moiety is wherein R, R', R. R. R. R. R', and R'' are each Substituted with one or more groupS. Selected from the group independently hydrogen or a Substituted or unsubstituted consisting of halogen, a C-C alkyl, C-C alkoxy, and Substituent Selected from the group consisting of C-Co phenyl. alkyl, C2-Coalkenyl, C2-Co alkynyl, aryl, C-Cocarboxy 4. The compound of claim 1 wherein R is hydrogen and late, C-Co alkoxy, C-Coalkenyloxy, C-Co alkynyloxy, R" is selected from the group consisting of C-Co alkyl, aryloxy, Ca-Co alkoxycarbonyl, C-Co alkylthio, C-Co C-Coalkenyl, and aryl. alkylsulfonyl and C-C alkylsulfinyl. 5. The compound of claim 4 wherein R' is phenyl or 15. The compound of claim 1 wherein L is an N-hetero vinyl. cyclic carbene ligand or a phosphine, and L'and L are each 6. The compound of claim 1 wherein X and X’ are each heterocyclic ligands. independently hydrogen, halide, or Selected from the group consisting of C-C alkyl, aryl, C-Co alkoxide, aryloxide, 16. The compound of claim 15 wherein at least one of Cs-Co alkyldiketonate, aryldiketonate, C-C carboxylate, L'and L is aromatic arylsulfonate, C-C alkylsulfonate, C-C alkylthio, 17. The compound of claim 15 wherein L'and L together C-C alkylsulfonyl, or C-C alkylsulfinyl, wherein X and form a bidenatate ligand. X" is each independently substituted or unsubstituted. 18. The compound of claim 1 at least one of L'and L is 7. The compound of claim 6 wherein at least one of X and a unsubstituted or Substituted heteroarene selected from the X' is substituted with one or more moieties selected from the group consisting of furan, thiophene, pyrrole, pyridine, group consisting of C-Co alkyl, C-Co alkoxy, and aryl, bipyridine, picolylimine, gamma-pyran, gamma-thiopyran, wherein the moiety is substituted or unsubstituted. phenanthroline, pyrimidine, bipyrimidine, pyrazine, indole, 8. The compound of claim 7 wherein the moiety is coumarone, thionaphthene, carbazole, dibenzofuran, diben Substituted with one or more groupS. Selected from the group Zothiophene, pyrazole, imidazole, benzimidazole, oxazole, consisting of halogen, C-C alkyl, C-C alkoxy, and phe thiazole, dithiazole, isoxazole, isothiazole, quinoline, bis nyl. quinoline, isoquinoline, bisisoquinoline, acridine, 9. The compound of claim 1 wherein X and X’ are each chromene, phenazine, phenoxazine, phenothiazine, triazine, independently Selected from the group consisting of halide, benzoate, C-C carboxylate, C-C alkyl, phenoxy, C-Cs thianthrene, purine, bisimidazole and bisoxazole. alkoxy, C-C alkylthio, aryl, and C-C alkyl Sulfonate. 19. The compound of claim 18 wherein at least one of 10. The compound of claim 9 wherein X and X’ are each Land L is a substituted or unsubstituted pyridine or a independently Selected from the group consisting of halide, substituted or unsubstituted pyridine derivative. CFCO, CHCO, CFHCO, (CH) CO, (CF)(CH)CO, 20. The compound of claim 18 wherein the substituted or (CF)(CH) CO, PhO, MeO, EtO, tosylate, mesylate, or unsubstituted heteroarene is Selected from the group con trifluoromethaneSulfonate. Sisting of: US 2003/0069374A1 Apr. 10, 2003 36

-continued NSir O rN isN CHO CH 2 N 'N 21 1. Y CH CH N(CH3)2 N e S e' CH N N O \ N21 N N N O 21 21 HC CH C) X N 2 Nch, N 1Schch, 21 NN N21 21 N 2N N 21 S e' Ol CH S N N 21 NN Y 21 N1a2N N HC N e' (H3C)3C N N 21 O N N NO2 21 N CH C(CH3)3 N 2N

N | N

NO2

CH 21 N

N N

rC N(CH3)2 and 21 NN S 2 O N | N

N(CH3)2 ( y (/ D \ / S.1."r 21. The compound of claim 1 wherein at least one of S O O L'and L is a unsubstituted or substituted heterocycle Selected from the group consisting of: US 2003/0069374A1 Apr. 10, 2003 37

24. A compound Selected from the group consisting of: N N N N O CN N O CO / NK--chPCys Y \ CCn CON (, C C CO CX C-CN N N N 2^

C CCOMe C C,s

PCys C luluN N l-N s \/ /\-/ly \ * =Y.

OCH Br NO N H N R P n \ / and 1N 21 PCy3 / \ % =c=- - wherein R is Selected from the group consisting of C-Co Cl V alkyl, aryl, ether, amide, halide, nitro, ester, pyridyl. o N Ph 22. A compound of the formula: N L R1 L R1 ^2. A ^2. A L-C=c, O L-yc=C=G X1 R X1 R wherein / \ C fy N-Ru-C=CH M is ruthenium; o Y. Y -CH3 X and X’ are each independently selected from the group 21 HC1 V consisting of halide, CFCO, CHCO, CFHCO, CH (CH) CO, (CF)(CH)CO, (CF)(CH) CO, PhO, N MeO, EtO, tosylate, mesylate, or trifluoromethane Sulfonate; / \ / \%.PCy3 L is any neutral electron donor ligand; N N c=e o o Cl L'and L are the same or different and are each a Substituted or unsubstituted heteroarene, and wherein L'and L'may be joined. R is hydrogen and R' is selected from the group consisting of C-Co alkyl, C2-C20 alkenyl, and aryl. 23. The compound of claim 22 wherein X and X’ are each Cl, L is (IMesH), L'and L are each independently a pyridine or pyridine derivative; R is hydrogen and R' is phenyl or vinyl. US 2003/0069374A1 Apr. 10, 2003

-continued -continued PC PC C. y3 C y3 1. 1. N-RuCECH N-RECECH V Ph

US 2003/0069374A1 Apr. 10, 2003 40

wherein -continued siMes Ph M is ruthenium or osmium; X and X’ are the same or different and are each indepen dently any anionic ligand; L., L', and L are the same or different and are each independently any neutral electron donor ligand; R and R' are the same or different and are each indepen dently hydrogen or a Substituted or unsubstituted Sub Stituent Selected from the group consisting of C-Co alkyl, C-Co alkenyl, C2-Co alkynyl, aryl, C-Co carboxylate, C-Coalkoxy, C-Coalkenyloxy, C-Co alkynyloxy, aryloxy, C2-Co alkoxycarbonyl, C-Co alkylthio, C-Co alkylsulfonyl, C-C alkylsulfinyl, and silyl. 26. The method of claim 25 wherein M is ruthenium; X and X’ are each independently selected from the group consisting of halide, CFCO, CHCO, CFHCO, (CH) CO, (CF)(CH)CO, (CF)(CH) CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethane Sulfonate; L is an N-heterocyclic carbene ligand or a phosphine; Land L are the same or different and are each a Substituted or unsubstituted heteroarene; R is hydrogen and R' is selected from the group consisting of C-Co alkyl, C2-C20 alkenyl, and aryl.

27. The method of claim 26 wherein X and X’ are each Cl, L is (IMesH) or a phosphine, L'and L are each indepen dently a pyridine or pyridine derivative; R is hydrogen and R" is phenyl or vinyl. 28. A method for the ring-opening metathesis polymer ization of a cyclic olefin comprising contacting the olefin with a compound of the formula

L R1 L R1 ^2. M ^2. M

L-C=c,X 1. R O L-C-C=X1. R wherein sIMES or IMesH is wherein

CH HC X and X’ are each independently selected from the group consisting of halide, CFCO, CHCO, CFHCO, (CH) CO, (CF)(CH)CO, (CF)(CH) CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethane Sulfonate; -(-)-CH HC L is any neutral electron donor ligand; Land L are the same or different and are each a Substituted or unsubstituted heteroarene; 25. A method for the metathesis of a cyclic or acyclic olefin comprising contacting the olefin with a compound of R is hydrogen and R' is selected from the group consisting the formula: of C-Co alkyl, C2-C20 alkenyl, and aryl. 29. The method of claim 28 wherein the olefin is Substi tuted or unsubstituted norbornene or a norbornene-type L R1 L R1 monomer or derivative therefrom. ^2. M ^2. M 30. The method of claim 29 wherein the olefin is Substi L'-- O L-y-c=t tuted or unsubstituted dicyclopentadiene. X1. R X1. R 31. The method of claim 29 wherein the olefinis a mixture of one or more Substituted or unsubstituted norbornenes or norbornene-type monomers or derivatives therefrom. US 2003/0069374A1 Apr. 10, 2003 41

32. A compound of the formula: ide, carboxyl, nitrosyl, pyridine, and thioether, N-heterocyclic carbene ligand or any derivatives therefrom. 38. The method of claim 37 wherein both Land L are L R1 L R1 either the same or different N-heterocyclic carbene ligands. ^2. M ^z. M 39. The method of claim 38 wherein the N-heterocyclic L-C=c, O L-ye-c= carbene ligand is Selected from the group consisting of: X1. R X1. R wherein R6 R7 R6 R. R. R7 M is ruthenium or osmium; R10-N N-R11 R10-N N-R11 X and X’ are the same or different and are each indepen N1 N1 dently any anionic ligand; OO OO L., L', and L are the same or different and are each R7 independently any neutral electron donor ligand; R is hydrogen or a substituted or unsubstituted substituent R10-NN=( N-R 11 Selected from the group consisting of C-C alkyl, N1 C-Coalkenyl, Ca-Co alkynyl, aryl, C-C20 carboxy late, C-C20 alkoxy, Ca-Co alkenyloxy, C2-Co alky nyloxy, aryloxy, C-C alkoxycarbonyl, C-C alky wherein R, R', R. R. R. R. R', and R'' are each lthio, C-Co alkylsulfonyl and C-C alkylsulfinyl, independently hydrogen or a Substituted or unsubstituted Substituent Selected from the group consisting of C-Co R" is Substituted or unsubstituted C-Coalkenyl. alkyl, C-Coalkenyl, C-Co alkynyl, aryl, C-Cocarboxy 33. The compound of claim 32 wherein R' is substituted late, C-Co alkoxy, C2-Coalkenyloxy, Ca-Co alkynyloxy, or unsubstituted vinyl. aryloxy, Ca-Co alkoxycarbonyl, C-Co alkylthio, C-Co 34. A method for the synthesis of a ruthenium or osmium alkylsulfonyl and C-C alkylsulfinyl. hexacoordinated metathesis catalyst comprising contacting a 40. The method of claim 35 wherein L is an N-heterocy ruthenium or osmium pentacoordinated metal carbene met clic carbene ligand, and L'and L are each heterocyclic athesis catalyst with a neutral electron donor ligand. ligands. 35. The method of claim 34 wherein the catalyst is of the 41. The method of claim 35 at least one of L'and L is a formula: unsubstituted or Substituted heteroarene selected from the group consisting of furan, thiophene, pyrrole, pyridine, bipyridine, picolylimine, gamma-pyran, gamma-thiopyran, L 1. L 1. X R a. R phenanthroline, pyrimidine, bipyrimidine, pyrazine, indole, 1: M 1 : M coumarone, thionaphthene, carbazole, dibenzofuran, diben L - C=c,1. O L - 1. =C=c, Zothiophene, pyrazole, imidazole, benzimidazole, oxazole, X R X R thiazole, dithiazole, isoxazole, isothiazole, quinoline, bis quinoline, isoquinoline, bisisoquinoline, acridine, wherein chromene, phenazine, phenoxazine, phenothiazine, triazine, thianthrene, purine, bisimidazole and bisoxazole, or deriva M is ruthenium or osmium; tives therefrom. 42. The method of claim 41 wherein at least one of L'and X and X’ are the same or different and are each indepen L is a substituted or unsubstituted pyridine or a substituted dently any anionic ligand; or unsubstituted pyridine derivative. L., L', and L are the same or different and are each 43. A method for the synthesis of a ruthenium or osmium independently any neutral electron donor ligand; hexacoordinated metathesis catalyst of the formula: R and R' are the same or different and are each indepen dently hydrogen or a Substituted or unsubstituted Sub Stituent Selected from the group consisting of C-Co alkyl, C-Co alkenyl, C2-Co alkynyl, aryl, C-Co carboxylate, C-Co alkoxy, C-Coalkenyloxy, C-Co alkynyloxy, aryloxy, C2-Co alkoxycarbonyl, C-Co alkylthio, C-C alkylsulfonyl and C-C alkylsulfi nyl, and silyl. comprising contacting a ruthenium or oSmium pentacoordi 36. The method of claim 35 wherein L, L'and L are each nated metal carbene metathesis catalyst with a neutral elec independently Selected from the group consisting of a mono tron donor ligand; wherein dentate, bidentate or tetradentate neutral electron donor M is ruthenium; ligand. X and X’ are each independently selected from the group 37. The method of claim 35 wherein L, L'and L are each consisting of halide, CFCO, CHCO, CFHCO, independently Selected from the group consisting of phos (CH) CO, (CF)(CH)CO, (CF)(CH) CO, PhO, phine, Sulfonated phosphine, phosphite, phosphinite, phoS MeO, EtO, tosylate, mesylate, or trifluoromethane phonite, arsine, Stibine, ether, amine, amide, imine, Sulfox Sulfonate; US 2003/0069374A1 Apr. 10, 2003 42

L is any neutral electron donor ligand; carbonyl, C-Co alkylthio, C-C alkylsulfonyl and L'and L are the same or different and are each a C-Cao alkylsulfinyl and silyl; and Substituted or unsubstituted heteroarene; and A is hydrogen, Si, Sn, Li, Na, MgX and acyl, wherein X is any halogen and B is Selected from the group R is hydrogen and R' is selected from the group consisting consisting of CC1, CHSOPh; CF; OR'; and of C-Co alkyl, C2-C20 alkenyl, and aryl. N(R')(R), wherein R is selected from the group 44. A method for polymerizing an olefin comprising: consisting of Me, CH5, i-CH7, CHCMes, CMes, contacting a compound of the formula: CH, (cyclohexyl), CHPh, CH norbornyl, CH-norbornenyl, CH, 2,4,6-(CH-)-CH (mesityl), 2,6-i-PrCH, 4-Me-CH (tolyl), 4-C-CH; and L R1 L R1 wherein R* and R are each independently selected X2. A X. A from the group consisting of Me, CH5, i-CH7, L-C=c, O L-C-C=G CHCMes, CMe, C.H. (cyclohexyl), CHPh, X1. R X1. R CH-norbornyl, CH-norbornenyl, CH, 2,4,6- (CH),C.H., (mesity), 2,6-1-PreC.H., 4-Me-CH4 (tolyl), 4-C-CH). with a compound of the formula: 45. The method of claim 44 wherein M is ruthenium; R11 R11 X and X’ are each independently selected from the group consisting of halide, CFCO, CHCO, CFHCO, R. l R (CH) CO, (CF)(CH)CO, (CF)(CH) CO, PhO, R9 X.y s A MeO, EtO, tosylate, mesylate, or trifluoromethane R8 B or B Sulfonate; R L is any neutral electron donor ligand; R10 R10 L'and L are the same or different and are each a Substituted or unsubstituted heteroarene; and a cyclic or acyclic olefin; R is hydrogen and R', R, R7, R, R, R', R'' are each independently selected from the group consisting of wherein hydrogen, C-Co alkyl, C2-Coalkenyl, and aryl; M is ruthenium or osmium; A is hydrogen and B is CCls. X and X’ are the same or different and are each indepen 46. The method of claim 44 wherein the olefin is a dently any anionic ligand; Substituted or unsubstituted norbornene or a norbornene type monomer or derivative therefrom. L., L', and L are the same or different and are each 47. The method of claim 44 wherein the olefin is Substi independently any neutral electron donor ligand; tuted or unsubstituted dicyclopentadiene. R,R,R,R,R,R,R'' and R'' are the same or different 48. The method of claim 44 wherein the olefin is a mixture and are each independently hydrogen or a Substituted or of one or more Substituted or unsubstituted norbornenes or unsubstituted Substituent Selected from the group con norbornene-type monomers or derivatives therefrom. Sisting of C-Co alkyl, C-Coalkenyl, C2-Co alkynyl, 49. The compound of claim 1 wherein at least one of L, aryl, C-C20 carboxylate, C-Co alkoxy, C2-Co alk Land L is an N-heterocyclic carbene ligand. enyloxy, C-Co alkynyloxy, aryloxy, C-Co alkoxy k k k k k